CS208118B2 - Fungicide means and method of making the active substances - Google Patents

Abstract

The new compounds of the formula I <IMAGE> in which R1, R2 and R3, independently of one another, denote halogen and two of the three substituents also denote hydrogen, X denotes an N atom or -CH= and T is methyl or ethyl and U is ethyl or propyl, including their plant-compatible salts with inorganic or organic acids and their metal complexes, are suitable as microbicides, in particular for combating phytopathogenic fungi. They can be employed together with suitable carriers in the form of plant protection agents.

Description

(54) Fungicidal product and process for the manufacture of active substances · 1

This invention relates to novel 1- _(1-p 3 dlsxslan-2-ymethyl) H-imidazslύ and -IHI ,, ^ "triazoles tubstituovených at positions 4 e 5 1,3-dIoxslanovéhs ring, which compounds are useful · annimikrobiální VLAST The invention also relates to a process for the preparation of these compounds and to phthicidal compositions containing said compounds as active compounds.

US Patent No. 732,829, filed October 15, 1976, and US Patent Nos. 3,575,999 and 4,079,062, disclose a series of 1- (2-aryl-1,3-dsoxslan-2-ylmethyl) -1H. -imidazoles and -1H-1,4-triazoles, and a series of 1- (2-aryl-1,3-disxslan-2-ylmethyl) -1H-imidazoles and -1H-1,2,4-traazoles, of which 1, The 3-disxslane residue is substituted with one alkyl group or two methyl groups. However, the compounds of this invention differ substantially from the above compounds by the presence of either two alkyl groups, one of which contains at least 2 carbon atoms, at the 4 and 5 positions of the di-oxoterone ring, or by the presence of a tetramethlene ring at these positions.

SUMMARY OF THE INVENTION The present invention provides novel 1- (2-agyl-1,3-disslan-2-ylmethyl) -1H-imidazoles and -1H-1,2,4-traazoles derivatives of formula I

in which

3

R, R and R 'are independently selected from the group consisting of hydrogen atoms and halogen, with a Tm at least one of syábolů B ^{1, R 2} and R represents a hydrogen ^ ^ Logen

Q is CH or N,

T represents a mettyl or ehypha group and

U stands for ehhi nbbo prppy group, or

T and U taken together form a tetamethyl glycol moiety, optionally substituted with up to two methylene groups, and their phytopharmaceutical acid addition salts, metal salt complexes, and stereochemically isomeric forms.

Preferred compounds are those compounds of the formula I 13 wherein R 2 and R ^J ^ alkyleneoxy means hydrogen, Cl "or Br and R is chloro or bromo.

preferred are composites of ^ CN ^ of formula ^I wherein ^{R2 is?} Cl ai> 12

R and Ro are hydrogen, and those compounds of formula I wherein R and R 'are chlorine and ^R is hydrogen.

Even more preferred compounds within the scope of the invention are those compounds of formula (I) wherein Q is N, and those wherein T and U represent a tert-butylene moiety, preferably a substituted tetamethylene moiety.

The most preferred compounds of the invention are those compounds of formula I wherein Q is N, T and U are substituted tetamethylene, R 'and R' are hydrogen, and R 'is chlorine, as well as compounds in which Q represents a nitrogen atom, T and U represent; A substituted radical, R and R ', represents the atoms of the diluent, and R' represents a hydrogen atom.

As used herein, the term "halogen" refers to fluorine, chlorine, bromine and iodine, and the term "propyl" refers to n-propyl and isopropyl.

As mentioned above, the invention also provides a process for the preparation of a compound of formula I, an antimicrobial composition comprising as an active ingredient an antimicrobial active compound of formula I, and a method of treating plant diseases using compounds of formula I.

Compounds of formula (I) may generally be prepared by reacting an azole of formula (II) wherein Q is as defined above and Me represents a hydrogen atom, i.e. a substituted ammonium ion, for example a tetalkylammonio group having 1 to 6 carbon atoms in each alkyl moiety. tгtllkytanrniciou group Laz 6 carbon atoms in each alkyl part, etc., or preferably a metal atom ňejvýhodnněl an alkali metal, e.g. sodium, potassium, etc., with a halide having the following formula III wherein R ^1, R ^{2, R} \ ^t and ^U mmaí with ^H ora defined and ^γ represents ha ^ ^ gene preferably chlorine, bromine or iodine. This reaction is possible by the following reaction scheme:

(II) (H1). 3

The reaction of the compound of formula II with the compound of formula III is preferably carried out in a relatively polar inert organic solvent, such as N, N-dimethylformamide, Ν, Ν-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and the like. with other inert solvents such as aliphatic or aromatic hydrocarbons, for example benzene, methylbenzene, dimethylbenzene, hexane, petroleum ether, chlorobenzene, nitrobenzene and the like. potassium. In this embodiment, the rate of reaction is increased. It is expedient to operate at an elevated temperature of from about 30 to 220 ° C, preferably from about 80 to 170 ° C. The reaction is carried out under reflux.

When Me is hydrogen, the reaction is carried out in the presence of a base. Suitable bases include alkali metal oxides, hydroxides, carbonates and acidic carbonates, as well as tertiary amines such as Ν, Ν-diethylethanamine, pyridine and the like. Because of the basic nature of the azole of Formula II, excess azole can be used as a reaction promoter.

In these and subsequent reactions, the reaction product may be isolated from the reaction medium and, if necessary, further purified by methods known per se, such as extraction, trituration, crystallization, chromatography, and the like.

Suitable salt forming acids are those which are well tolerated by plants and physiologically tolerated acids, such as inorganic acids such as hydrochloric, hydrobromic, hydroiodic, sulfuric, phosphoric, phosphonic, nitric and the like, as well as organic acids such as trifluoroacetic acid, trichloroacetic acid, benzenesulfonic acid. , methanesulfone and the like.

Complexes of compounds of formula I with metal salts may be obtained by reacting an azole of formula I with an organic or inorganic metal salt such as a hydrohalide, nitrate, sulfate, phosphate, 2,3-dihydroxybutanedioate and the like copper, manganese, zinc, iron and similar transition metals, which metals may be present in any valency.

Stoichiometrically defined metal salt complexes can be prepared by dissolving a compound of formula I in a water-miscible solvent (e.g., warm ethanol, methanol, 1,4-dioxane or Ν, Ν-dimethylphonamide) and adding an aqueous solution to the solution. a solution of the desired metal salt such as copper sulfate pentahydrate, manganese nitrate tetrahydrate, ferric chloride hexahydrate and the like.

The foregoing is for illustration only and is not intended to limit the scope of the invention in any way.

The intermediates of formula (II) used as starting materials in the reactions described above are generally known in the art.

Intermediates of formula (III) may be prepared by methods known in the art for the preparation of such or analogous compounds, such as by acetylation of the appropriate acetophenone derivative of formula (IV) below with the appropriate 1,2-diol of formula (V) below. This reaction can be described by the following reaction scheme:

(conversion of residue

2 3

In the above reaction scheme, R, R, R, T and U are as previously defined and L represents a hydrogen atom or the radical Y. When L represents a hydrogen atom, it is converted to a halogen atom by a known halogenation process either before, during or after acetalization.

The acetalization reaction is simply carried out by stirring and heating the reactants in a suitable inert solvent such as benzene, methylbenzene and the like, preferably in the presence of a catalytic amount of a suitable acid such as 4-methylbenzenesulfonic acid and the like. reaction ·

Alternatively, acetals of formula III may be prepared from other cyclic or aliphatic acetals by reacting the acetals with an excess of the 1,2-diol of formula V corresponding to the desired acetals. When T and U represent a tetramethylene radical optionally substituted by up to two methyl substituents, the corresponding cis- and trans-1,2-cyclohexanediols as well as mixtures containing both isomers can be used as the 1,2-diol of formula V to give cis- and / or trans-forms of the acetals of formula III.

It is apparent from the general formula I that the compounds of the invention contain at least 3 asymmetric carbon atoms in the molecule, namely the carbons at positions 2, 4 and 5 of the dioxolane nucleus, and that they can therefore exist in different stereochemically isomeric forms. The present invention includes all stereochemically isomeric forms of the compounds of formula (I), as well as their phytopharmaceutically acceptable acid addition salts and metal salt complexes.

The diastereomeric racemates of formula (Ϊ) can be separated by conventional methods. Suitable methods which may be used in the present case include, for example, selective crystallization and chromatographic separation, for example column chromatography.

Since the stereochemical configuration is already firmly fixed in the intermediates of formula (III), it is also possible to separate the diastereomeric racemates at this stage and prepare the corresponding forms of the compounds of formula (I) as described above by separating the intermediates into diastereomeric racemates. are described above for the separation of diastereomeric racemates of compounds of Formula I.

The compounds of the formula I have a very advantageous spectrum of antimicrobial activity, which makes them useful for the protection of crops without causing any undesired side reactions.

Examples of useful plants that can be treated in accordance with the invention are cereals, corn, rice, vegetables, sugar beet, soy, peanuts, fruit trees, ornamental plants, vine hops, cucurbits (cucumbers, pumpkins, melons) ), eggplants such as potatoes, tobacco and tomato, as well as bananas, cacao and rubber.

The compounds of formula (I) may be used to inhibit or suppress fungal growth on the aforementioned or related plants, or parts thereof (for example, on fruits, flowers, leaves, stems or stems, tubers and roots), against fungal attack Protected and newly grown parts of treated plants. The compounds of the invention are active against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Erysiphaceae, Fusarium, Venturia, Helminthosporium), Basidiomycetes such as in particular rust (e.g. Puccinia), Fungi imperfecti (e.g. Monilialesyc etc. Cercospora and Botryteteses) belonging to the Phycomycetes class, such as Phytophthora and Plasmopara. The disclosed compounds can further be used as seed dressings for treating seeds (for example, fruits, tubers, grains) and seedlings to protect them from fungal infestation and against fungi occurring in the soil.

Botrytis fungi (Botrytis cinerea, Botrytis allii) cause widespread economic damage as they cause fungal diseases of grapevine, strawberries, apples, onions and other fruits and vegetables.

The compounds of the formula I can be used either independently or in admixture with suitable carriers and / or additives. Suitable carriers and additives may be solid or liquid and are well known in the art. These include, for example, natural and regenerated mineral materials, solvents, dispersants, surfactants, adhesives, thickeners, coatings, or mechanical taoids.

The concentration of the active ingredient in commercial compositions can range from about 0.1 to about 20 grams

%.

For application, the compounds of formula (I) may be formulated, for example, into the following formulations (for which appropriate active compound concentrations are indicated in brackets):

solid compositions: dusts (up to 10%), granules, coated granules, impregnated granules and homogeneous granules, pellets (from 1 to 80%);

liquid compositions: - (a) water-dispersible concentrates, wettable powders and pastes (25 to 90% in commercial preparations, 0,01 to 15% in applicable solutions), emulsifiable and soluble concentrates (10 to 50% in commercial preparations, 0) 0.01 to 15% in applicable solutions);

b) solutions (0.1 to 20%), aerosols.

If desired, compounds of formula I to increase the range of suitable jnýfai combined with pesticides, such as fungicides, bakkeeicidy, ittd ^to kicidy, akaaicidy,. herbicides, rossiin growth regulators, etc.

The invention is illustrated by the following examples, which are intended to limit the invention in any way.

A. Examples of active ingredient preparation

Example '

To a mixture of 86 g (1.3 mol) of 85% powdered potassium hydroxide and 100 g (1.45 mol) of 1,2,4-tetrazoles in 1000 ml of Uimedylsulfoxide are stirred for 8 hours at 145 ° ^C after stirring ^{. p} s dog mites ^{to give} 3 ⁶ 3 ^{g (1,} 025 mo ^ ^C T / 2-tanls brsшmteyl-2- ^(2,4-n diihlosfd У) -5-dthyl-4-methyl-hУ - 1 After the addition was complete, the dark brown reaction mixture was heated with stirring for an additional 6 hours, then cooled, taken up with 3 liters of 1,1'-oxybitethane and 6 liters of water, shaken and the layers were shaken. odděěí. the organic layer is for ^ n into non-rdlní reaction, dried, and fittaaci the odppaí. give a very viscous brown oil, which after under reduced pressure to give 271 g ⁽⁷⁷ 3%) very viskóznCho hollow oil of temperature ¹ boiling 36 and ¹⁵² ° C ^{/ 0,} and ^P 4, ^the esters st .mu.m zkyš tax. After trotátsbtném following reinstallation of a mixture of 2,2-hexane sxybispropttu from ^{I ka b} Ily Kyst Alic ^ ^[2 - ^{(2, 4} -dichlsr dnyl ^f) - ⁵ -Me ⁴ -dthyl- ^DTH гl- ^1, 3-disxoltn ylmedhyll-2-1H-112,44tritzsl mp 109-113 ° C.

The following compounds are summarized in an analogous manner:

compound number Q R ¹ R ² T no isomerism in positions salt melting point (° C) 1.1 N Cl Cl CH ₃ ^C 2 ^H 5 cis - 81.1 1.2 N Cl Cl ^CH 3 c ₂ h ₅ cis / trans - 109 to 113 1.3 N H Cl CH ₃ ^C 2 ^H 5 cis / trans HNO ₃ - 1.4 N Cl Cl CH ₃ cis / trans HNO ₃ 146.6 1.5 N H Cl ^CH 3 ηο, α. cis / trans - - 1.6 N Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 cis HN0 ₃ 160.9 1.7 N H Cl ^C 2 ^H 5 c ₂ H ₅ cis - - 1.8 N Cl Cl ^C 2 ^H 5 cis HCl - 1.9 N H Cl ^C 2 ^H 5 ^пС з ^ cis - - 1.10 N Cl Cl CH ₃ c ₂ H ₅ cis CuCl ₂ - 1.11 N Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 cis Mn _{(NO3) 2} - 1.12 N Cl Cl CH ₃ cis ZnCl ₂ - 1.13 N Cl Cl CH ₃ Cjl cis ZnCl ₂ - 1.14 N Cl Cl CH ₃ ^C 2 ^H 5 cis Mn _{(NO3) 2} - 1.15 N Cl Cl CH ₃ c ₂ h ₅ cis / trans FeCl ₃ - 1.16 N Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 C8 CuCl ₂ - 1.17 N Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 cis ZnCl ₂ - 1.18 N Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 C8 FeCl, et al - 1.19 N Cl Cl c ₂ H ₅ ®2®5 · cis / trans CuCl ₂ - 1.20 CH Cl Cl CH ₃ c ₂ h ₅ cis - oil 1.21 CH H Cl CH ₃ ^C 2 ^H 5 cis / trans - viscous substance 1.22 CH Cl Cl ^CH 3 cis HN ° 3 - 1.23 CH H Cl c ₂ H ₅ c, h ₅ cis - • - 1.24 CH Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 C8 H ₂ Sat ₄ - 1.25 CH Cl Cl c ₂ H ₅ nCjH? cis / trans - viscous substance 1.26 CH Cl Cl CH ₃ ^C 2 ^H 5 cis (COOH) ₂ - 1.27 CH Cl Cl ^CH 3 c ₂ h ₅ cis Fe01 ₃ - 1.28 CH Cl Cl CH ₃ ^C 2 ^H 5 cis CuCl ₂ - 1.29 CH Cl Cl c ₂ H ₅ ^C 2 ^H 5 C8 CuCl ₂ - 1.30 CH Cl Cl CH ₃ nCjHy cis CuCl ₂ - 1.31 CH Cl Cl ^CH 3 ^C 2 ^H 5 cis Mn _{(NO3) 2} - 1.32 . CH Cl Cl ^CH 3 ^C 2 ^H 5 cis / trans CuCl ₂ - 1.33 CH Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 cis Mn (NO ₃ ) ₂ - 1.34 CH Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 cis ZnCl ₂ - 1.35 CH Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 cis / trans CuCl ₂ 1.36 CH Cl Cl ^C 2 ^H 5 ^C 2 ^H 5 cis / trans '- oil

Example 2

A solution of 27 g (0.1 mol) of 2,4-dichlorophenacyl bromide, 17.5 g (0.15 mol) of industrial 1,2-cyclohexanediol (cis-trans-isomers) and 0.5 g of 4-methylbenzenesulfonic acid in 200 µl Methylbenzene is refluxed with a water separator for 8 hours. · After cooling. No. 7,208,118 the resulting solution was washed with an aqueous solution of acidic carbonate. sodium hydroxide and evaporated. Evaporation of the excess 2,4-dichloreenacylboomidu under reduced pressure (1.3 Pa) in an oil bath of TE · ^{P 1} Lot 5 ⁰ ° C, with from ^{I to 30 g} é ^ o vislcozn oil obsalihjíc jpřevážnč ^ o cis-2 ssomer - (Bromoethane) -2- (2,4-dichlorophenyl) hexamethylbenzene-dioxol.

A mixture of 11 g (0.1 mol) of potassium terc.lutoxidu and 7 g (0.1 mol) of 1,2,4-irtazslj in dimeetylfommamidu stirring and zadívání to ^130C instance ^ID, and ^{30 g (0, 08} 2 mol) ^^ rcmmehyD-2- (2,4- ^ 1. ^ 10 ^^ 411 hheaalyrdrolenzodioxolu. After the addition the reaction mixture was ls ^d ^! ^ c ^{h 20 h} MIC Odin ^h and at temperatures of ⁰ to ¹ 3 The residue was taken up in water and extracted with 1,1'-oeybis ethane / ethyl acetate, and the organic layer was separated and dried to give 25 g of a viscous gum residue which was stirred at ¹⁴⁰ ° C. starting with c) chromatography on a silica gel column using dichloromethane as eluent.

The pure fractions were and the solvent was SPPO odppai give · to obtain 12 g of yellow residue iinatého pгlslkl ^also formed by anaayticiých and spectroscopic data [2- _(2> 4-dLch lorfeeyl) hexa-hldoSlnzedSdxseo2-ylletlvlJ "1H-1,2- , 4-trazzoeem.

Example 3

A. Analogous to the first part of Example 2, replacing the technical 1,2-

-cyklsheetndiolu omen) irtes ^1,2-d cykloheetn Isle irtes- afford [2- (2,4-dichlorfeell) heeti'hrlroOlnzoZSdxseol ylmeteylll1H-1,1,2-triazole as a viscous oil.

B. 5 g (0.072 mol) of potassium carbonate and 4 g of pure potassium hydroxide were refluxed for 1 hour in absolute ethanol. The ethanol was evaporated. under reduced pressure, and the 1,2,4-triazole potassium salt formed is taken up in 200 ml of dihydroxy sulfide. After addition of ¹⁸ 5 g ^(0,0 moles of ^5-trans-1 I ² - ^{2) of} the hexa ^hyd rsbeneo IOOO ^e o22y ^{l hl} IIlethy -1H-1,1,4-triazole reaction mixture was stirred for ⁸ Todini on zadívání ¹ 4 ⁰ C, and ^p is cooled and dilute ^d i ¹ liter of water. The aqueous solution was extracted several times with 1.1% ^of water, the organic layers were separated. and dried. 4 ml of 65% nitric acid are added to the extract while stirring, whereupon white crystals precipitate. OddiltlOáánío these crystals yielded 15 grams traes- [2- (2,4-dichlsrf enyDheeahy ^{l ro} lnre ^ZS oxsl- ^s - ^{2 h} III ^of rel-1,2,4-l1H ⁴ г atolsn ^{i e} the trátj te ^p ture mp ^153-1 55 ° C.

The following cis-ketones are prepared in an analogous manner:

- R1 ch ₂ / b - R ² JX O IN h umy— ) compound R ¹ R ² r3 Q salt / base temperature number melting point (° C) 2.1 Cl Cl H CH - ' vilklzeí fabric 2.2 H Cl H CH - - 2.3 H Br H QH - · - 2.4 Cl H Cl CH - - 2.5 Cl Cl H N - viscous substance 2.6 H Cl H N - - 2.7 Br Br H N -. - 2.8 Cl Cl 5-C1 N

compound number R ¹ · R ² R ³ Q salt / base melting point (° C) 2.9 . ^{NO. 1} CL H CH CuCl ₂ 2.10 ’Cl Cl H N СиСЦ - 2.11 Cl Cl H CH Mi (NO ₃ ) 2 - 2.12 Cl Cl H N (N0 ₃ ) 2 -

The following trans-ketals are prepared in an analogous manner.

compound number R ¹ R ² r3 Q salt melting point (° C) 2.13. Cl Cl H CH HNO ₃ 185 to - 190 (Z) 2.14 H Cl H CH - 2.15 Cl Cl H N HNO3 153 to 155 (Z) 2.16 H Cl H N - 2.17 Cl Cl 5-C1 N - 2.18 Cl Cl H CH CuClg 2.19 Cl Cl H CH № (N03) 2 2.20 Cl Cl H N ' CUCI2 2.21 Cl Cl H N № (N03) 2

The following mixtures of cis- and trans-ketel are also prepared in an analogous manner:

1 ----- N ch ₂ cf R ¹ —R ^{2 4} r3 r / 'r ⁵ compound number r1 R2 R ³ Q R ^{4 r5} salt / base melting point (° C) 2.22 Cl cl H N ^GH 3 H - viscous oil

B. Examples of composition and formulation

Example 4

Dust

The following ingredients are used to prepare a) 5% and b) 2% dusts:

(a) 5 parts of active substance, parts of talc;

(b) 2 parts of active substance, part of highly dispersed silicic acid and parts of talc.

The active ingredient is mixed with the carriers and the mixture is ground. The resulting preparation can be processed to a dust suitable for direct application.

Example 5

Granulate

The following components are used to prepare the 5% granulate:

parts of the active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.25 parts of polyethylene glycol and parts of kaolin (particle size 0.3-0.8 mm).

The active ingredient is mixed with epichlorohydrin, the mixture is dissolved in 6 parts of 2-propanone, and then polyethylene glycol and cetyl polyglycol ether are added. The resulting solution was sprayed onto kaolin and the 2-propanone was evaporated in vacuo.

The microgranulate thus prepared is preferably used to combat soil fungi.

Example 6

Wettable powder

The following ingredients are used to prepare a) 70%, b) 40%, c) and d) 25% and e) 10% wettable powder:

(a) 70 parts of active substance, parts of dibutylnaphthalenesulfonate sodium, parts of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde condensation product (3: 2: 1), parts of kaolin, parts of chalk;

(b) 40 parts of active ingredient, parts of sodium lignin sulphonate, parts of dibutylnaphthalenesulfonic acid sodium salt, parts of silicic acid;

(c) 25 parts of active substance,

4.5 parts of calcium lignin sulphonate,

1.9 parts of a mixture of chalk and hydroxyethylcellulose (1: 1),

1.5 parts of sodium dibutylnaphthalenesulfonate,

19.5 parts of silicic acid,

19.5 parts of chalk

28.1 parts of kaolin;

(d) 25 parts of active substance;

2.5 parts of isooctylphenoxy-polyethyleneethanol,

1.7 parts of a mixture of chalk and hydroxyethylcellulose (1: 1),

8.3 parts of sodium aluminum silicates,

16.5 parts of diatomaceous earth, .46 parts of kaolin;

»

(e) 10 parts of active substance, parts of a mixture of sodium salts of saturated sulphated fatty alcohols, parts of a naphthalenesulphonic acid-formaldehyde condensation product and 82 parts of kaolin.

The active ingredient is intimately mixed with the other excipients in a suitable mixer and ground in a suitable grinding machine. A wettable powder is obtained with excellent wettability and suspending ability. This powder can be diluted with water to a suspension of the desired concentration, which is mainly used for foliar application.

Example 7

Emulsifiable concentrate

The following ingredients are used to prepare 25% emulsifiable concentrate:

parts of the active substance,

2.5 parts of epoxidized vegetable oil,

% Of a mixture of an alkylarylsulfonate and a fatty alcohol polyglycol ether, parts of dimethylformamide and

57.5 parts of dimethylbenzene.

By diluting this concentrate with water, emulsions of the desired concentration can be prepared which are particularly suitable for foliar application.

C. Examples of biological activity

Example

Activity against Cercospora personata (= Cercospora arachidicola) (cercosporosis) on peanut plants Week-old peanuts are treated with a spray containing 0.02% active ingredient prepared from a wettable powder. After about 12 hours, the treated plants are infected with a conidia suspension of the fungus. The contaminated plants are incubated for about 24 hours at 22 ° C and high relative humidity (greater than 90%) and then transferred to greenhouses. The fungal infestation is evaluated on the twelfth day after infection, based on the number and extent of spots on the plants. Compared to untreated plants, there is only limited or no fungal growth on the plants treated with the compound of formula (I).

Compounds 1.1, 1.2, 1.6, 1.10, 1.11, 1.13 to 1.19 and 2.5 inhibit fungal growth in concentrate or 0.002%.

Example 9

Activity against Puccinia graminis (rust grass) in Wheat

a) Residual finger-effect

Wheat plants are sprayed with a preparation containing 0.06% of the active ingredient and made of a comminutable powder from 6 days after the start. After 24 hours, the treated plants are infected with a uredsspore fungus suspension. After incubation at ityřieettssmihodinové relative humidity of ^95-100% and ^p s at about ²⁰ ° C, the plants further uchovávvjí in glass te ^p s ^p ture of about ²² ° C. After ^{12 days} of ^p ^ Filiač in ^ ^ i ODN development kupe ^to rust. The compounds of formula (I) have been found to be potent fungicides in this test. efficiency. Compounds i. 2.5 and 2.15 inhibit fungal growth even at 0.006%.

(b) Systemic effect

Roosi's wheat is shaken 5 days after sowing with a preparation containing 0.006% of active ingredient (proportional to the soil volume), which is made from the dark-colored powder. After 3 days, the treated plants are infected with a fungal uredospore suspension. After incubation at ityřiceiOtsmihsdiosvé relative yl ^ ^d mod ear axis 95, and ^f КО teplott% and about 20 ° C, the plants ^can le · uchováávaí in tkleo ^Cart with at teptatt zftr 2 ^ and ² ° C. Evolution vs. ^P e in ^the rust-odnocuje ¹² days after infection.

The compounds of formula I have been found to exhibit potent fungicidal activity in this test. Compounds Nos. 1.1, 1.2, 1.6, 1.10, 1.11, 2.5, 2.15, and 2.22 completely inhibit fungus growth, Compounds Nos. 2.5 and 2.15 inhibit fungal growth in the bloodstream of the fungus. 0.0006% (based on soil volume).

Example 10 ·

Residual protective effect of Venetia inanqujlit (apple scab) on apple seeds

Apple seedlings 10 to 20 cm high are inoculated with a preparation containing 0.06% active ingredient, first of a dark powder. After 24 hours, the treated plants are infected with a suspension of cationic fungi. Roosiiny first inkubuuí at relative humidity 90 and ^{00% of} i, and ^p is ¹⁰ days and in uchováávaí tkleo ^Cart with ^p ^ s tepto ^{20 and 2} 4 ° C. After ¹ 5 days after infection, the good advantage ^ i of the disease. .

The compounds of formula I have been found to exhibit potent fungicidal activity in this test. Compounds No. 1.1, 1.2, 1.6, 1.10, 1.11, 2.22 and others inhibit fungal growth at 0.006% concerination, Compounds No. 2.5 and 2.15 even after 0.0006% end.

They did

Residual protective effect of ^р гоН Podosplhaera (fall of apple) on apple sheds0More

Apple seedlings 15 cm in height are sprayed with a preparation containing 0.06% active ingredient prepared from a wettable powder. After 24 hours the treated plants are infected with a suspension of the fungus and konnddí infkovvané uiUováávaí plants in a greenhouse at 70% relative ^vi ^ ^u ^ <^ s ^ ^s ^: s mod ^d uc u ^h at ²⁰ ° C. ^U ^ Rozs8 Chom shall assess the 12 days after infecting a ^ i.

The compounds of formula (I) have been found to exhibit potent fungicidal activity in this test. Compounds No. 1.1, 1.2, 1.6, 1.10, 1.11, 2.5, 2.15 and others inhibit fungal growth at 0.006%.

208118 12

Example 1 12

Effectiveness against Erysiphe graminis (fallen grass) on barley

a) Residual protective effect

8 cm high barley plants are sprayed with a preparation containing 0.02% active ingredient prepared from a wettable powder. After 3-4 hours, the treated plants are dusted with conidia of the fungus. Infected barley plants are then placed in a greenhouse at a temperature of about 22 ° C and the extent of disease is evaluated 10 days after infection.

b) Systemic effect

Spraying 0.006% active ingredient (the amount of active ingredient corresponds to the soil volume) prepared from a wettable powder is treated with barley plants about 8 cm high, taking care not to contact the aerial parts of the plants with the spray. After 48 hours, the plant treatment is dusted with conidia of the fungus. Infected barley plants are further stored in a greenhouse at 22 ° C, and the extent of the disease is evaluated after 10 days.

In experiments a) and b), the compounds of formula I completely inhibit the growth of the fungus. Compounds Nos. 1.1 to 1.4, 1.6, 1.8, 1.10 to 1.19, 2.1, 2.2, 2.4, 2.5, 2.6, 2.9, 2.10, 2.13, 2.15, 2.18 and 2.22 inhibit fungal growth in experiment a) even at a concentration of 0.002 %. Compounds Nos. 1.1 and 1.2 inhibit fungal growth in experiment (b) at concentrations of 0.002% and Compounds Nos. 2.5 and 2.15 at concentrations of 0.0002%.

Example 13

Activity against Botrytis cinerea (Gray mold) on broad beans

Bean plants, about 10 cm high, are sprayed with a preparation containing 0.02% active ingredient prepared from a wettable powder. After 48 hours, the treated plants are infected with a fungal conidia suspension. After three days of incubation at 95-100% relative humidity and a temperature of 21 C. ^{In the} evaluation of the disease.

The compounds of formula I have been found to completely inhibit fungal growth. Compounds No. 1.1, 1.2, 1.4, 1.6, 2.1 and 2.13 show total efficacy even at a concentration of 0.006% ·

Claims (16)

SUBJECT OF THE INVENTION What is claimed is: 1. A fungicidal composition comprising an antifungal effective amount of an azole compound comprising an inert derivative of the general formula: a carrier and an effective amount thereof. I (I) in which R ¹ , R ² and R ³ are independently selected from the group consisting of at least one of R, R and R is CH or N, methyl or ethyl, and hydrogen and halogen are halogen U represents an ethyl or propyl group, or Together, U forms a tetramethylene radical, optionally substituted with up to two methyl groups, and / or its phytopharmaceutically useful acid addition salts, metal salt complexes or stereochemically isomeric forms. 2. A composition according to claim 1, wherein the active ingredient is a compound of formula (I): R, R, ^RJ and Q are as defined in point 1, T is methyl or ethyl, U represents an ethyl or propyl group and / or a phytopharmaceutically usable acid addition salt, a metal salt complex or a stereochemically isomeric form thereof. 3. A composition according to claims 1 and 2, characterized in that it comprises as active ingredient a compound of the formula I wherein R ¹ and R are hydrogen; R 2 represents a chlorine or bromine atom. 4. A composition according to claim 3, characterized in that it comprises as active ingredient a compound of the formula I wherein R ¹ represent hydrogen and R represents a chlorine atom. 5. A composition according to claim 3, wherein the active ingredient is a compound of formula (I) wherein R and R are chlorine and R is hydrogen. 6. A composition according to claim 4, wherein the active ingredient is a compound of formula (I), wherein Q is nitrogen. 7. A composition according to claim 5, wherein the active ingredient is a compound of formula (I) wherein Q is a nitrogen atom. 8. A composition according to claim 6, wherein the active ingredient is a compound of formula I wherein T and U are an optionally substituted tetramethylene moiety. 9. A composition according to claim 7, wherein the active ingredient is a compound of formula (I) wherein T and U are optionally substituted tatramethylene. 10. A composition according to claim 8, wherein the active ingredient is a compound of formula (I) wherein T and U are unsubstituted tatramethylene. 11. A composition according to claim 9, wherein the active ingredient is a compound of formula (I) above wherein T and U are unsubstituted tetramethylene. 12. A composition according to claim 1 comprising an inert carrier and, as active ingredient, an antifungal amount of a compound selected from the group consisting of [2- (2,4-dichlorophenyl) hexahydrobenzodioxol-2-ylmethyl] -1H-1,2,4 triazole and its phytopharmaceutically useful acid addition salts, metal salt complexes and stereochemically isomeric forms. 13. A composition according to claim 1 comprising an inert carrier and, as an active ingredient, an antifungal amount of a substance selected from trans208118. [2- (2,4-Dichlorophenyl) hexahydrobenzodioxol-2-ylmethyl] -1H-1,2,4-triazole and its phytopharmaceutically usable acid salts, metal salt complexes and stereochemically isomeric forms. , 14. A composition according to claim 1 comprising an inert carrier and a. as active ingredient an effective quantity antifvngálnč substance selected from the group c zatarnujcí Bis- [2- (2,4-dichlofeayyl) eeaaУ7drobenztdioχol 2-ylmθt YRL ^] -1 H- _1,2-J 4 triaztl fytofaraaceuticky uρotřebiielaé and its addition salts acids, metal salt complexes and stereochemically isomeric forms. 15. A composition according to claim 1, which comprises an inert carrier and, as an active ingredient, an antifungal active amount selected from the group consisting of [2- (2,4-Dithltriphenyl) -4-methyl-4-methyl-5-methylbenzimiditol-2-]. ylethyl] -1H- _1,2,4 -triazole and its phytopharmaceutically acceptable acid addition salts, metal salt complexes and stereochemically isomeric forms. 16. A method according to claim 1, wherein the compound of the formula (II): EMI3.0 wherein: EMI3.0 [0025] wherein: EMI2.0 [0030] Q is as defined above and Me represents a hydrogen atom, a tetrasubstituted ammonium ion, a trillkylamine residue in which each alkyl moiety contains 1 to 6 carbon atoms or a metal atom, and reacts with a compound of formula III (III) wherein: Y represents a halogen atom and. The remaining general symbols are as defined above, in a relatively polar inert organic solvent at elevated temperature, where, when Me is hydrogen, the reaction is carried out in the presence of a base, whereupon the product obtained is converted to a phytopharmaceutically usable acid addition salt. , a complex with a metal salt or stereochemically isomeric form.