HU192262B - Fungicid and process for production of metall complexes of derivatives of-2-phenoxi-2-triazolil etanole /or etanone/ serving as active substance - Google Patents

Abstract

The present invention relates to a fungicidal agent comprising the metal complex of 2-phenoxy-2-triazolyl ethanol (v. Ethanone) and the preparation of the active compounds. The metal complexes of 2-phenoxy-2-triazolyl ethanol (v. Ethanone) can be prepared by reacting phenoxytriazolyl ethanol (on) derivatives and the metal salt of the aromatic carboxylic acid in a solvent. -1-

Description

The present invention relates to a fungicidal agent and to a process for the preparation of metal complexes of 2-phenoxy-2-triazolylethanol (v. Ethanone) derivatives as an active ingredient. '

The present invention provides a novel fungicidal agent which provides sufficient protection against various phytopathogenic fungal pathogens even at low application rates or concentrations.

Certain 1,2,4-triazole derivatives, such as 1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) 3,3-dimethylbutane-2, are known or a 2: 1 complex thereof with copper (II) chloride has a fungicidal effect as disclosed in U.S. Patent Nos. 2,201,063 and 2,423,987, respectively. Disclosure documents in the Federal Republic of Germany, or equivalent, are disclosed in U.S. Patent Nos. 165,782 and 171,714 respectively. Hungarian patents.

It is also known in the literature that the compounds of formula II, which are the starting materials for the process of the invention, already have fungicidal activity per se. However, these substances, especially at low application rates or concentrations, have a reduced efficacy and narrower spectrum of action.

It is known in the art that complexes of triazolyl derivatives of formula II with metal halides more precisely with metal chlorides are also fungicidal (German Patent Publication No. 2,423,987 and Hungarian Patent Application No. 171,714). . These complex derivatives replace at least 80%, i.e. up to 20%, of the triazole active ingredient from the triazole active ingredient; in spite of the encouraging greenhouse tests, their efficacy has been significantly reduced during small field trials in the field, and therefore these derivatives have not become widespread in practice.

It is an object of the present invention to provide metal complexes of novel 2-phenoxy-2-triazolylethanol (v. Ethanone) derivatives that can reduce the triazole-containing active substance utilization by 40-50%. This not only replaces the expensive triazole derivative with a cheap metal salt without reducing efficiency or narrowing the spectrum of action, but also reduces the burden on nature of active triazole derivatives.

We have found that the formula I is new

Metal complexes of 2-phenoxy-2-triazolyl ethanol (v.etanone) derivatives - where

Me: copper, zinc, manganese, tin or magnesium,

X: halogen,

Q: CO or C (OH) H,

Y ¹ : halogen (C 1 -C 3 alkoxy) carbonyl, nitro, or sulfo group,

Y ² : represents a halogen atom or a hydroxy group, n has a value of 0.1 or 2, m has a value of 0.1 or 2, m 'has a value of 0 or 1, k has a value of 1,2,3 or 4 and has 2 or 4 excellent fungicidal properties.

It has now been found that metal complexes of 2-phenoxy-2-triazolyl ethanol (v. Ethanone) slides of formula I can be prepared from a triazole compound of formula II wherein X, Q and n are as defined above in formula III. by reacting a metal salt of an aromatic carboxylic acid, wherein Me, Y ¹ , Y ² are 1, m is as defined above, in the presence of a solvent.

The starting materials of formula (II) and their preparation are known. The following compounds of formula II may be used as starting materials in the process of the invention:

X 4-C1 n 1 Q co 2,4-Cl ₂ 2 co - 0 co 4-Br 1 co 4-F 1 co 2-C1, 4-Br 2 co 3-C1 1 CH (OH) 2,4,6-Cl ₃ 3 CO 4-NH ₂ 1 co 2,3- (CH ₃ ) ₂ 2 co 4-NO ₂ 1 co 4-CH ₃ O- 1 CH (OH) 4-C ₆ H _s -SO ₂ 1 CO 4-C ₆ H _s -CO- 1 CO 4-CF ₃ -O 1 CO

The metal salts of the general formula (III) used for complexing are also known. In the formula (III), Me is preferably II. and IV. and la, Ha, and IVa, Va, Via, Vlla and Villa, which are readily complexed metals, especially copper, zinc, manganese, tin, or magnesium. The metal salts may include benzoic acid and substituted derivatives as acid residues. These salts are known and readily prepared, for example, from an inorganic acid salt of the metal and an alkali metal salt of the aromatic carboxylic acid.

In the process of the invention, the solvent is water or an inert organic solvent. As organic solvents, alcohols such as methanol, ethanol, ketones such as acetone, ethers such as diethyl ether, dioxane, tetrahydrofuran can be used.

The reaction temperature can be varied within a relatively wide range without substantially altering the quality or quantity of the product. The active ingredient is prepared at a temperature of 5 to 50 ° C, preferably 20 to 25 ° C.

According to the invention, the metal salt of formula (III) is reacted with an equimolar amount of a complexing triazole compound of formula (II), preferably in accordance with the degree of oxidation of the metal therein. A slight excess of any of the reactants will not affect the quality or quantity of the product. The fungicidal active ingredient is recovered by conventional organic chemical methods.

Compositions containing metal complexes of the 2-phenoxy-2-triazolyl ethanol (v. Ethanone) derivatives of the present invention have extremely strong fungicidal activity and a broad spectrum of activity. The preparations alone or as in combination with other active ingredients, phytopato-21 of the Phycomyoetes, Ascomycetes, Basidiomycetes and Deuteromycetes classes of the Eumycotine subfamily can be used effectively

192,262 genes against fungal pathogens. The formulations have both contact, protective, preventive and systemic, curative and protective properties. eradication effect. They are absorbed through both the root and the leaf and are therefore widely used - e.g. for dressing, soil treatment, spraying. They can be used successfully as a spray after the infection has occurred.

The compositions of the present invention are particularly effective against powdery mildew of the order Erysiphalea of the Ascomycetes class. Their use is recommended

- Sphaerotheca fuliginea and Erysiphe cichoracearum in cucumbers;

- Podosphaera leucotricha in apples;

- in wheat and barley Erysiphe graminis f. sp .; tritici and f. sp. hordei;

- Unicinula nocator in vines;

- peppers and tomatoes against Léveillula taurica.

Some of the compositions of the invention inhibit the growth of certain plant pathogens and other bacteria.

The compositions may also be used against rust fungi of the Basidiomycetes class, uredinales, especially Puccinia graminis, Puccinia stricformis, Puccinia recondita.

The formulations may be applied by conventional land or air routes in said culture

12.5-1500 g active ingredient / ha, respectively. 1-5000 mg active ingredient per liter spray. Neither unpleasant odor nor skin irritation makes their application difficult. The low application rate allows the pesticide load on the ecosystem to be reduced.

The preparations are not phytotoxic to crop plants.

To broaden or broaden the spectrum of action. may be combined with other fungicides to enhance the effect. In addition, they may be mixed with insecticides, acaricides, regulators, etc. The said combinations may be provided in the form of a tank mix, but the various active ingredients may also be combined in the formulation.

The active compounds of the present invention can be formulated into standard formulations such as solutions, emulsions, suspensions, pastes and granules. Said formulations are prepared in a manner known per se, for example, by incorporating the active compounds with known excipients such as liquid solvents and / or solid carriers, optionally surfactants such as emulsifying and / or dispersing agents and / or foaming agents and, if necessary, other ingredients. with formulation aids. When using water as a carrier, an organic cosolvent may also be added. Liquid solvents in addition to said water include aromatic hydrocarbons such as benzene, toluene, xylene and alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, methylene chloride, and mineral oil fractions, alcohols such as butanol or glycols and their ethers or esters. They can be used. In addition to the above, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone and highly polar solvents such as dimethyl sulfoxide, dimethyl formamide are particularly suitable. Solid carriers include natural stone flour and such artificial materials as kaolin, montmorillonite, talc, quartz, attapulgite, silica, or highly dispersed silica, alumina and synthetic silicates. Non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkyl sulfates, alkyl sulfonates, aryl sulfonates, and the like are emulsifying and / or foaming and / or other formulation auxiliaries. protein hydrolysates, sulfite impurities, methylcellulose and lignin as dispersants.

The compositions generally contain from 0.1 to 90% by weight, preferably from 1 to 50% by weight, of the active ingredient.

The active compounds may be in the form of compositions or other known active compounds, e.g. in the form of preparations containing fungicides, insecticides, acaricides, nematicides, herbicides, wild-type repellents, growth regulators, fertilizers and soil conditioners, or in ready-to-use forms thereof, such as solutions, emulsions, suspensions, pastes or granules. Application is by conventional means such as spraying, dusting, dressing etc.

When used as foliar fungicides, the ready-to-use composition will generally contain from 0.1 to 0.001% by weight, preferably 0.05 to 0.001% by weight of the active ingredient.

The active compounds of formula I, like triazole derivatives in general, also exhibit micromicidal and regulatory activity.

The invention is illustrated by the following examples.

Example 1

Bisph 1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one] copper (H) -bis (3,5-dinitrobenzoate) production

To a stirred solution of copper (II) bis (3,5-dinitrobenzoate) (24.3 g, 0.05 mol) in tetrahydrofuran (150 ml) was added 29.4 g (0.1 mol) of 1- (1.2) A solution of -triazol-1-yl (-1,4-chlorophenoxy) -3,3-dimethylbutan-2-one in tetrahydrofuran (100 ml) was added dropwise. After the addition was complete, the slurry was stirred at room temperature for another 3 hours, then the precipitate was filtered off and washed with a little tetrahydrofuran. Water (600 mL) was added to the filtrate to give additional precipitate. The precipitate was collected and dried.

After drying, 51.1 g (95%) of bis [1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one] copper (II) bis (3,5-dinitrobenzoate) is obtained, m.p. 185-188 ° C. Among the starting materials, 1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one is a known compound, the preparation of which is known in the art. .

The other starting material is copper (II) bis (3,5-dinitrobenzoate). This was prepared by 4.0 g (0.1 g)

A solution of 3,5-dinitrobenzoic acid (21.2 g, 0.1 mol) in sodium hydroxide (192 262 mol) and water (75 ml) was dissolved. After complete dissolution, a solution of copper (II) dichloride dihydrate (8.5 g, 0.05 mol) in water (25 mL) was removed. After stirring for 10 minutes, the precipitate was allowed to stand for 1 hour, then filtered, washed with water and dried.

Example 2

Bis [1- (1,2,4-triazol-1-yl) -1- (2,4-dichlorophenoxy) 3,3-dimethylbutan-2-one] copper (II) bis [( 2-methoxycarbonyl) benzoate]

Copper (21.1 g, 0.05 mole) (II) bis [(2-carbo- ^methoxy-15 phenyl) benzoate] was dissolved in 50 ml of water. 32.8 g (0.1 mol) of 1- (1,2,4-triazol-1-yl) -1- (2,4-dichlorophenoxy) -3,3-dimethylbutane are added dropwise with stirring. 2 in 75 ml of ethanol. After the addition, the slurry was stirred for a further 2 hours, then the precipitate was filtered, washed and dried. Yield: 45.3 g (84%) of bis [1- (1,2,4-triazol-1-yl) -1- (2,4-dichlorophenoxy) -3,3; dimethylbutan-2-one; ] copper (II) bis [(2-methoxycarbonyl) benzoate], respectively. 85-7 ° C. ⁵

Example 3

Bis [1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan-2-ol] copper (II) bis (2-) Preparation of hydroxy-5-sulfobenzoate (24.9 g, 0.05 mole) of copper (II) bis (2-hydroxy-5-sulfobenzoate) in water (29.9 g) 0.1 mol) of 1- (1,2,4-triazol-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan-2-ol previously dissolved in 50 ml of ethanol. After stirring for 2 hours, the solvent was distilled off in vacuo and the residue was recrystallized from ether to give 47.4 g (87% yield) of bis [1- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) 3,3-Dimethylbutan-2-ol] -Cu (II) bis (2-hydroxy-5-sulfobenzoate) is obtained. 115-120 ° C.

Example 4

Bis [1- (1,2,4-triazol-1-yl) -1- (4-bromophenoxy) -3,3-dimethylbutan-2-one] copper (II) bis (4-fluoro-) Preparation of Benzoate Benzoyl copper (II) bis (4-fluorobenzoate) (17.1 g, 0.05 mol) was slurried in ml of ethanol and 33.8 g (0.1 mol) of 1- (1.2) , 4-Triazol-1-yl) -1- (4-bromophenoxy) -3,3-dimethylbutan-2-one in 130 ml of ethanol. The slurry was stirred for 4 hours then filtered, washed and dried to give 49.9 g of bis [1- (1,2,4-triazol-1-yl) -1- (4-bromophenoxy) -3,3-dimethylbutane] -on] copper (II) bis (4-fluorobenzoate), m.p.

By working according to any of the above examples, the following compounds of formula (I) are prepared.

example Me X n Q k Y ¹ Y ² m m '1 Op 'C 5th Cu 4-C1 1 co 2 2,4-Cl ₂ 2 0 2 131-2 6th Cu 4-C1 1 C / OH / H 4 3,5- (NO ₂ ) ₂ - 2 0 2 ' 165-68 7th Cu 4-C1 1 CO 2 3-NO ₂ 4-C1 1 1 2 185-90 8th Cu 4-C1 1 CO 2 - 2 ΟΗ 0 1 2 93-6 9th Cu 4-C1 1 CO 2 2-C00-CjH ₇ - 1 0 2 130-5 10th Cu 4-C1 1 CO 2 2-C1 - 1 0 2 113-6 11th Cu 4-C1 1 CO 2 4-C1 - 1 0 2 128-30 12th mg 4-C1 1 CO 1 2,4-Cl ₂ - 2 0 2 160 decays 13th sn 2,4-Cl ₂ 2 CO 2 2,4-Cl ₂ 2 0 4 74-5 14th mg 4-C1 1 co 1 4-C1 - 1 0 2 124-7 15 Cu 4-C1 I co 2 3,5- (NO ₂ ) ₂ 4-C1 2 1 2 165-70 16th Mn 4-Br 1 co 2 3,5- (NO ₂ ) ₂ 4-C1 2 1 2 188-9 17th Cu 4-Br 1 C / OH / H 3 4-C1 - 1 0 2 176-9 18th Zn 2,4-Cl ₂ 2 CO 2 2-C1 - 1 0 2 108 19th Cu 4-C1 1 CO 2 4-F - 1 0 2 194-7 20th Cu - 0 C / OH / H 4 2-C1 - 1 0 2 108-10 21st Zn 4-Cl 1 CO 2 - - 0 0 2 118-22 22nd Zn 4-C1 1 CO 2 2,4-Cl ₂ - 2 0 2 103-06

192 262.

Example 23

25% dispersible powder.

25%. No. 5 Example 5, 5% highly dispersed silica, 6% lignin sulfonate, 1% alkyl naphthalene sulfonate, 63% kaolin.

Example 24

50% dispersible powder.

50% of the compound of Example 1, 10% highly dispersed silica, 6% lignin sulfonate, 2% fatty acid methyl lauride, 32% silica.

Example 25

80% Dispersible Powder 80% according to Art. Example 13, Na% 13% highly dispersed silica, 6% lignin sulfonate 1% aliphatic sulfonic acid.

Example 31% dusting agent.

1% of No. 13 Example 10, 10% kaolin, 89% talc.

Example 32

40% suspension concentrate.

40% of No. 1 example compound, 3% Na-alkyl naphthyl sulfonate formaldehyde condensate, 4% polyoxyethylene triglyceride alkylaryl sulfonate mixture, 1% silicone antifoam, 0.1% xanthan gum (anionic polysaccharide), 5.0% ethylene glycol, 46.9% water.

Example 33

25% oily suspension concentrate Example 6 6% Emulsogenic N (HOECHST Fatty Alcohol Polyethylene Glycol Ether), 34% Water, 35% Paraffin Oil.

Example 26

25% pulp.

25% of No. 16 Example 10, 10% Lignin Sulfonate, 1% Alkyl Naphthyl Sulfonate, 0.5% Rhodamine B (Dye) (Dialkylaminoxanthene, BASF, ROMPP 1984) 63.5% Kaolin

Example 27

10% wet suspension.

10% of No. 14 Example 5, 5% lignin sulfonate.

0.5% Rhodamine B (dye), 84.5% caseinate solution.

Example 28

20% wet pulp.

20% of No. 8 Example compound 0.5% Rhodamine B (dye)

10.0% z isopropyl alcohol, 69.5% dimethylsulfoxide.

Example 29

10% emulsifiable concentrate.

10% of No. 12 Example 5, Oxetylated Polyaryl Phenyl Phosphate 5% Orthophosphoric Acid Mono (Dioxyethylaryl) Ester Neutralized with 5% Triethanolamine, 40% N-Methyl-2-Pyrrolidone 40% Xylene.

EXAMPLE 30% Dry Powder.

25% of No. 20 Example compound 2% Rhodamine B (dye)

3% refined mineral oil, 70% kaolin.

Example 34

Protection against wheat dust In standard cultivation pots, we plant unmodified "Mv-4" wheat seed into the standard soil mixture. At least 10 plants are left as breeding pots after emergence. Double leaf, if necessary

We grow the plants until 4-6 leaves. Subsequently, the composition of Example 23 was then sprayed in the usual manner. For field sprayers mounted on a field sprayer frame (eg Tee Jet TG or TK type), the plants are sprayed with the appropriate concentration of spray. After 24 hours, it is artificially infected with wheat powder (Erysiphe graminis f. S. Tritici). The dishes were placed in a random block arrangement in 5-7 replicates in a greenhouse at 20 ° C. After 12-14 days, we assess the onset of symptoms on the Hinfner scale (Hinfner, K., Békési, F .: National Species Experiments pp. 113. Budapest, 1971). The active ingredients of the preparation, the active compound concentrations and the results of the inhibition of infection are shown in Table I below.

Table 1

Erysiphe graminis sp. degree of tritici inhibition in contact preventive manner

Active ingredient Inhibition%

10 pg / ml conc. 5 pg / ml conc. Example 1 85 80 Example 3 23 10 Example 5 83 97 Example 6 88 56 Example 7 52 29 Example 9 27 21 Example 10 78 81

192 262

Table I (continued)

agent Inhibition% 10 pg / ml conc. 5 pg / ml conc. Example 11 76 90 Example 12 46 37 Example 13 81 82 Example 15 74 60 Example 16 48 31 Example 17 70 66 Example 19 67 60 Example 20 74 63 Example 21 74 57 Example 22 83 46 ARC. formula number (is- 80 78

Example 35

Systematic action against wheat dust

For plants grown in Example 34, the compositions are poured over the soil surface of the pots to systematically examine the soil through the soil. Concentration is based on soil volume. Irrigation is carried out according to the needs of the plant. The active ingredients, concentrations and results of the formulations are shown in Table II. See Table 1.

II. Table 35

Systemic effects of active substances through soil

infections »

The active ingredient is 2.50 µg / ml l, 25 µg / ml 0.625 pg / m ⁴

Example 1 5.3 ± 3.9 ab ⁴⁴⁴ 10, 5 ± 3.5 bcdl5.0 ± 2.2d 40 Formula V (known) 2.3 ± 1.7 a 4.5 ± 3.3 ab 8.3 ± 4.1 abed ARC. formula (known) ⁴⁴ 26.3 ± 5.7 c 36.5 ± 7.6 f 33.8 ± 7.3 f untreated 56.2 ± 8.4 45 szd _5% ~~ 6.82 ⁴ Concentration gg active / ml soil volume

* ten times the concentration, ie 2.50 12.5 and 6.25 pg / ml, according to ⁴⁴⁴ Duncan's (Duncan Multiple Rank Test) candidates with the same letter do not differ by P - 95% probability ^{W4 +} If if the difference between the values is greater than the tolerable error given by SZD _px , then there is a real difference between the two values.

'· 55

Example 36

Curative effect against wheat flour

For curative testing, the procedure is the same as in Example 34, but the plants are inoculated for 2 days before spraying. Evaluation was performed on the 14th day after infection. The active substances, their concentrations and results are shown in Annex III. table.

III. spreadsheet

Curative effect of active substances

infection »

The active ingredient is _the concentration of _the active ingredient in gg / ml

25 12.5

50.3 ± 5.2 c

5.3 ± 1.3 a of Example I

Formula V (known) 13.8 ± 5.7 beds

VI. (known ⁴ ) untreated SZD, "

10.3 ± 1.7 ab 22.3 ± 5.0 d 18.8 ± 1.5 cd 19.03 ± 3.4cd 54.0 ± 8.5 c 50.8 ± 2.5 c

51.0 ± 3.4 c

7.29 ⁺ ten times the concentration, ie 500, 250 and 125 g / ml

Example 37

Effect against cucumber powder

In standard breeding pots, we plant unginned "Kecskemét bőtermő" cucumber seeds in horticultural soil mixture.

As plants, 2 plants are left after emergence. We grow the plants up to 4 leaves, if necessary up to 6 leaves. As usual, we spray the leaves and spray the plants with a spray gun until they flow. After 24 hours, the cucumber powdery mildew (Sphaerotheca fuliginea), the plants are uniformly blown from a spore suspension (10 ⁵ spores / ml). Place the culture pots at 24 ° C in a random block arrangement in a greenhouse.

Symptoms were evaluated after 14 days according to Spencer's method (Crop Protection Agents, Biological Evaluation, N.R. No Farlano, Academic Press p. 455, 1977).

The concentrations and results of the active ingredients of the formulations are shown in Table IV. See Table 1.

ARC. spreadsheet

Systemic effects of active substances on cucumbers

• Infection » agent concentration of the active ingredient in gg / ml 50. 25 12.5 Example 1 4.5 ± 2.4 a 14.0 ± 7.0 bed 22.0 ± 6.0 de Formula V l, 0 ± 7.6 ab 12.5 ± 3.7 abc 22.3 ± 4.4 de (known) VI. formula 60.5 ± 3.3 f 58.0 ± 9.3 f 53.5 ± 4.3 f (known) ⁴ ! untreated 88.0 ± 1.6 SZDj * 8.09

⁺ ten times the concentration, i.e. 500, 250 and 125 pg / ml

Example 38

Systemic action against soil cucumber powdery mildew. The percutaneous absorption test for cucumbers was carried out as in Example 35. The results are summarized in Table V.

192 262

Table V.

Absorption of active substances through cucumber soil

Infection%

The active ingredient is the concentration of the active substance in the soil pg / ml 2.50 1.25 0.625

3.8 ± 3.3 ab of Example 1 15.3 ± 8.1 cde 22.3 ± 4.3 ef V (known) 0.0 ± 0.0 a 2.5 ± 3.3 ab 18.5 ± 8.7 but «“ í? ⁰ 76.8 ± 3.8 gh 71.0 ± 6.5 g 74.8 ± 5.7 g ⁺ ten times the concentration, ie 25.0, 12.5 and 6.25 pg / ml

Example 39

Protection against barley powdery mildew

In standard cultivation pots, we plant unginned "VICTORIA" barley seed in a standard soil mixture. At least 10 plants per plant pot are left. After emergence, the plants are grown to 4-6 leaf age. Hereinafter, no. example. The results are shown in Table VI. See Table 1.

VI. spreadsheet

Contact effect against barley flour

Infection% agent concentration of the active substance in pg / ml 50 25 12.5 Example 1 5.2 ± 2.0 a 6.0 ± 2.0 a 11.7 ± 3.2 a Formula V (known) 8.7 ± 1.5 8.3 ± 3.3 a 13.0 ± l 0a VI. kepi. (known) ⁺ 23.3 ± 13.3 b 27.3 ± 4.7 b 27.7 ± 2.1 b untreated 56.7 ± 2.3

* ten times the concentration, ie 500, 250 and 125 g / ml

Example 40

Absorbing effect against barley powdery mildew.

The results of the soil absorption study are presented in Annex VII. Table ·.

VII. spreadsheet

Absorption through barley in soil

infection%

The active ingredient is the concentration of the active substance in the soil pg / ml 2.50 1.25 0.625

Example 1 3.3 ± 2.3 b 10.3 ± 5.9 in 9.3 ± 2.1 in

V (known) 0.7 ± 0.6 a 2.3 ± 1.5 ab 9.3 ± 2.1 into

VI. (known ⁺ ) 25.7 ± 3.1 d 23.7 ± 9.1 22.0 ± 4.6 d 'untreated 51.04 ± 8.2 ^SZP 5K 7.06 ⁺ , 0 12.5 and 6.25 pg / ml

Example 41

Field wheat dust protection

In the open air, "Mv-4" is sown with conventional agrotechnical techniques. In late autumn and early winter, the edge of the hatched wheat field is artificially infested with wheat powder (Erysiphe graminis f. S. Tritici). In spring, plots of 3.5 x 4 m are selected on the uninfected interior. Plots were randomized in a block arrangement with one untreated buffer plot between each plot. We manage the stock according to the plant protection technology regulations. After the last treatment

On day 21, infection is evaluated according to the Hinfner Scale. The results are shown in Table VIII. See Table 1.

Active Ingredients VIII. field inspection of Table agent Infection% mean and (standard deviation) concentration of active substance in kg / ha 0.75 0.375 Example 1 Example 5 Formula V (known) untreated 24.00 (1.41) a 31.50 (3.54) ab 36.50 (6.36) abc 46.00 (4.24) cd 33.50 (3.54) abc 46.00 (4.24) cd 60.00 (1.41) d

We summarize the main advantages of the present invention. The metal complexes of the 2-phenoxy-2-triazolyl-ethanol (v. Ethanone) derivatives produced by the process of the present invention reduce the use of the triazole-containing active ingredient, thereby reducing the burden on nature of such active ingredient;

- a more economical product can be produced because the price of the product decreases;

Metal complexes of the 2-phenoxy-2-triazolyl ethanol (v, ethanone) derivatives of the invention

- easy to produce

- the products made from them are well-handled and easy to use.

Claims (2)

CLAIMS 1. A fungicidal agent comprising a metal complex of a 2-phenoxy-2-triazolylethanol (v. Ethanone) derivative of formula (I) as an active ingredient. Me copper, zinc, manganese, tin, magnesium, X is halogen, Q is CO or (C / OH) H, Y ^{1 is} halogen, (C 1 -C 3) alkoxy, carbonyl, nitro or sulfo, Y ^{2 is} halogen or hydroxy, n is 0.1 or 2, m is 0.1 or 2, and if m is 2, Y ¹ is other than alkoxycarbonyl or sulfo, 192,262 m 'is 0 or 1, k is 1,2,3 or 4, 1 is 2 or 4 in an amount of 0.1 to 90%, preferably 1 to 50% by weight, the remainder being carriers, such as solvents, preferably aromatic hydrocarbons, and / or solid carriers, preferably natural stone flour or artificial materials of this kind, and surfactants, preferably emulsifiers and dispersants. A process for use as an active ingredient in a composition according to claim 1 of formula (I) For the preparation of metal complexes of 2-phenoxy-2-triazolyl-ethanol (v. Ethanone) derivatives, wherein Me, X, Q, Y ¹ , Y ² are as defined in claim 1, n, m, m ', 1 and k characterized in that (II) is ^5-triazole derivative of formula - wherein X, Q and n is as defined above - with a metal salt of formula (III) - wherein Me, Y ^1, Y ^2, A, m, m ', 1 are as defined above - 5 to 50 ° C - preferably 20 to 50 "C temperature, - solvent - ⁰ sen preferred water or an organic solvent, preferably an alcohol - acid.