CS253745B2 - Fungicide and process for preparing active compound - Google Patents

Description

It is furthermore known that the triazole derivatives of the general formula II are known

CH ₃

which can be used as starting materials in the process according to the invention are fungicidally active. However, the efficacy and spectrum of action of these compounds is particularly satisfactory, especially at the lower amounts and concentrations.

Finally, it is known that complexes of the triazole derivatives of the general formula II with metal halides, in particular with metal chlorides, are fungicidally active (cf. German Patent Specification No. 24 23 987 or U.S. Pat. No. 171,714). These complexes contain at least 80% of the triazole derivative, which also means a maximum of 20% of the triazole derivative. the effect of these complexes in the open fields, despite good results in the greenhouse, is very small and therefore the use of these active substances could not be extended.

SUMMARY OF THE INVENTION It is an object of the present invention to provide novel metal triazole complexes, whereby the use of triazole derivatives is to be reduced by 40 to 50%. This would make it possible to estimate an economically highly available triazole derivative with a cheap metal salt, as well as to reduce the burden on nature with an effective triazole derivative.

The fungicidal composition according to the invention contains as active ingredient a metal complex of the formula I having at least one tri-zolyol.

(AND)

where Me means copper, zinc, manganese, tin or magnesium X means atom halogen,

means a group of the formula CO or CH (OH), is halogen, C _L _ ₄ alkoxykdrbonylovon group iitoosknpiíln or sulfo, is hydrogen, halogen or Uydroxyskupinn Nam sign of zero, 1 or 2, sludge sign 1, 2, 3 or 4 and the integer mmei is zero and 6.

A process for the preparation of an active compound of the formula (I) of the triazole of the formula (II) comprises reacting a derivative

(II.) Wherein X, Q and n are as hereinbefore defined, with a metal salt of the drug carboxylic acid of formula III

Wherein Me, Y, Y, m, 1 and p are as defined above.

The reaction is carried out at a temperature between 5 and 50 ° C, in particular at 20 to 25 ° C, in the presence of a diluent, preferably water or an organic solvent, such as an alcohol.

It has been found that the novel metal salts of the formula I are particularly effective as fungicides. Derivatives triazole of formula II used as starting materials I are known or can be produced according to known methods and methods. As examples of compounds of formula II named compounds, where it means X n Q 4-C1 1 'CO 2,4-C12 2 WHAT - 0 what 4-Br 1 what 4-F 1 what 2-Cl, 4-Br 2 what 3-C1 1 CH (OH) Metal salts used as a further starting material of formula III they are also known.

In formula III, Me is the metals of II. and IV. the main groups, as well as from Ia, IIa and IVa to VIIIa, the subgroups of the periodic system, which in addition tend to form complexes. Me is in particular copper, zinc, manganese, tin or magnesium. As the acid-derived moiety, these metal salts may contain benzoic acid and substituted derivatives thereof. These salts are known and can be easily obtained by reacting the corresponding inorganic metal salts with the alkali metal salts of carboxylic acids.

Suitable diluents for the process according to the invention are water as well as organic solvents. These include, in particular, alcohols such as methanol and ethaned, ketones such as acetone, ethers such as diethyl ether, dioxane or tetrahydrofuran.

The reaction temperature can be varied over a wide range without affecting the quantity or quality of the end product. Generally, the temperature is between 5 and 50 ° C, especially between 20 and 25 ° C.

In carrying out the process according to the invention, the starting materials are used in equimolar amounts. The oxidation number of the metal ion in the metal salts of the general formula is taken into account

III. Excess of one or the other reaction component does not bring any significant advantages. The fungicidal active compounds can be isolated by methods customary in organic chemistry.

The novel metal impingers of the general formula (I) show a particularly high activity and have a broad spectrum of activity. The active compounds obtainable by the process according to the invention can be used, alone or in combination with other active compounds, with good results in anti-phytopathogenic fungi from Pnycommccees, Ascomyccees, Basidiomycetes and Deuteromycetes of the order Eummyerina.

The new active substances have a contact, protective, preventive and systemic, curative or eradicative effect. The new active substances absorb roots and leaves and can be used in a wide range, for example in seed treatment, soil treatment and spraying. The novel active compounds can also be used as a spraying agent with a good result even after infection.

Especially effective are the new active compounds for the general population such as Erysiphales of the Ascomy-yetes family. These active compounds can be used to inhibit Sphatrothetinig and Erysiphe cichoracearum in cucumbers, Podosphaera leucotricha in apple trees, Erysiphe iraminis f. Sp. ^! tritici and f. sp. hordei in barley and wheat, Inicinule necator in grapevine, as well as Leesšllula tanrica in pappicas and tomatoes.

The active compounds may furthermore be used for the production of fungi such as Basidiomycetes of the group Kredinales, in particular Pucciniacete in various types of cereals, such as Puucinia iraminis, Puccinia strioSruis, Puucinia meaditta.

The new active ingredients prevent the reproduction of certain pests and lattices.

The active compounds produced by the process according to the invention can be used in proportions in the amount of 12.5 to 1500 g of active substance per hectare or in a concentration of 1-5000 mg of active substance per liter per field or in air.

Their use is not difficult because they are odorless and do not cause skin irritation. The lower amounts used in the menu offer a burden on nature.

The active substances obtainable by the process according to the invention are not phytotoxic to crop plants.

In order to broaden or increase the efficacy spectrum, the active ingredients which are syrobable by the process of the present invention can be mixed with other fungicides, other acaric agents as well as rosslin growth regulators. These commodities may be used in the form of reservoir nets, but they are also possible in their formation.

The active compounds can be converted into the customary formulations such as solutions, suspensions, pastes and granules. These compositions are prepared in a known manner, for example by mixing the active ingredients with a filler such as an oily liquid solvent and / or a solid carrier, optionally with a surfactant such as an emulsifier and / or dispersing agent and / or a suds suppressor, as well as conventional formulation aids.

If water is used as filler, for example, organic solvents can also be used as co-solvents. Suitable liquid solvents are, in addition to water, aromatic hydrocarbons such as benzene, toluene, xylene or alkyl naphthalenes, chlorinated aromatic or tertiary hydrocarbons such as chlorobenzene, and benzene chlorides, as well as petroleum dessillation fractions, alcohols such as butanol or glycol, as well as their ethers and esters, ketones such as acetone, aenhhetylkntsn, aenhhutylbutylket.sn or cyclohexanone, strongly polar solvents such as НууПЬуУзпufoxide and diaethylSoraaaid.

Suitable solid carriers are natural or synthetic stone meal, such as coco, ammonium silos, fats, quartz, attapuucine, diatomaceous earth and highly dispersed silica, alumina and synthetic silicates.

As eauugační agent and / or foaming agent to prevent and / or further formulation auxiliaries suitable nonionic and anionic emuU ^g ator such polyoxyethylnnestery maatných kyssein, pslyoxyetУylennthnry rlitaiCtýýcУ alcohols alkylsuufáty, rltylsulfsnáty; arylsulfonates, as well as egg white hydrolysates, dispersants, sulfuric liquor, cellulose and lignite.

The compositions generally contain between 0.1 and 95% by weight of active ingredient, preferably between 1 and 50% by weight of active ingredient.

The active ingredients may be used alone or in admixture with other active ingredients, such as fungicides, insecticides, acaricides, non-inocides, herbicides, plant growth regulators, wash fertilizers or soil improvers, in their compositions as well as in ready-to-use forms. Suitable solutions, such as solutions, emulsions, suspensions, pastes or granules.

The use is carried out in a known manner, such as, for example, by spraying, treatment of a meeting or the like.

The koonenration of the active ingredient in the formulations to be used may vary from 0.001 to 0.1% by weight of active ingredient, preferably from 0.001 to 0.05% by weight, when used as fungicides per leaf.

In addition, the new active substances, like other triazole derivatives, also exert a microbial-suppressing effect and a plant growth-inhibiting effect.

The invention is illustrated by the following examples.

Example 1

Bi8- [1- (1,2,4-triazoo-1-yl) -1- (4-chlorophenoxy) -3,3-dioethylbutan-2-one] -deed-3,5- (dinitrobenzoate)

To a solution of 24.3 g (0.05 mol) of the 3,5-dinittobenzic acid copper salt in 150 ml of tetrahydrofuran is added dropwise a solution of 29.4 g (0.1 mol) of 1- (1,2,4-triazole-1-ol) with stirring. yl) -1- (4-chlorophenoxy) -3,3-dioethylbutan-2-yne in 100 ml of tetrahydrofuran.

After the addition was complete, the mixture was stirred at 0 ° C for 3 hours, then the precipitate obtained was aspirated and washed with a small amount of tetrahydrofuran. Water (600 ml) was added to the filtrate to precipitate additional solids.

The precipitate obtained is collected and dried. There was thus obtained 51.1 g (95% of theory) of bis-1- (1,2,4-trizol-1-yl) -1- (4-chlorophenyl) -3,3-dioethylbutan-2-one] -odide. - (3,5-nitrobenzate), m.p. 185-188 ° C.

The 1- (1,2,4-triazol-1-yl) -1- (4-chlorophenyl) -3,3-dioethylbutan-2-one used as the starting material is a known compound.

3,5-dinitobenzenesulfonic acid, necessary as a further starting material, is prepared from 21.1 g (0.1 mol) of 3,5-dinitobenzic acid by dissolving in a solution of 4.0 g (0%). , 1 mol) of sodium hydroxide in 75 ml of water. After complete dissolution, the cupric salt was precipitated with a solution of 8.5 g (0.05 mol) of cupric chloride dihydrate in 25 ml of water. The pellet was further stirred for 10 minutes and allowed to stand for one hour. The salt is then filtered off with suction, washed with water and dried.

Example 2

Bis- [1 '(1,2,4--Triaz ^ l ^ -l ^ l-yl) -1- (2 ₁ 4-nichltrfentxy) -3,3-nioenhylbutan-2-one] -měě (II) - (2-methoxycarbonylbenzoate)

Dissolve 21.1 g (0.05 mol) of the sodium salt of 50 ml of water in 50 ml of water and add dropwise with stirring dropwise the solution 32; 8 g (0.1 mol) of 1- (1,2,4-triazsl-1-yl-1- (2'-dichlorophentxy) -3,3-dioethylbutan-2-one in 75 ml of ethanol .

After the addition was complete, the batch was stirred for two hours, the precipitate was filtered off with suction, washed and dried.

45.3 g (84% of theory) of bis- [1- (1,2,4-triazol-1-yl) -1- (2,4-dichlorophenoxy) -3,3-dimethylbutan-2-one] are obtained. - copper (II) - (2-methoxycarbonylbenzoate), m.p. 85-87 ° C.

At la

Dissolve bis- [1- (1,2,4-triazcoil-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan-2-ol (1) -sulfonyl alicylate in water (24), 9 ml (0.05 mol) copper sulfosalicylic acid salt and add (0.1 mol) 1- (1,2,4-triazazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutane-2- After stirring for 2 hours, the solvent was distilled off under reduced pressure and the residue

In 50, 29.6 g ethanol.

is recrystallized from ether.

47.4 g (87% of theory) of bis-Q1 (1,2,4-triazol-1-yl) -1- (4-chlorophenyl) -3,3 * dimethylbutan-4-ol-copper (II) -sulfonyl-licylais were obtained. mp 115-120 ° C.

Example 4

Bis- [1- (l, 2,4-Sr гагоа-- ^yl) -l · - ^(4-b rom ^{phenoxy yl)} -3, ^3-di- methyl-butan-2-one] ^- Copper (IlHMhorbencoát)

17.1 g (0.05 mol) of copper (II) funorbenzoic acid are added to 80 ml of ethanol and a solution of 33.8 g (0.1 mol) of 1- (1,2,4-trilzol-11-yl) - is added. Of 1- (4-bromophenoxy) -3,3-dimethylbutan-2-one in 150 ml of ethanol.

The precipitate was stirred for four hours, filtered off with suction, washed and dried. There were obtained 49.9 g BLS - ^ - l '(1,2,4-irilcol-yl) -1-N- (4-bromophenoxy) - ^{3,3-dimethyl-yl]} .buSan 2-ONJ-mёě (II) 1- (4-fluorobencoate), m.p. 194-197 ° C.

The following compounds of formula I can be prepared analogously:

Table

Example Temperature

no. Me X n Q to Y ¹ Y ² m 1 melting ° i 5 Cu 4-Cl 1 WHAT 2 2,4-Cl H 2 2 131-132 6 Cu 4-Cl 1 what 2 3,5-NO ₂ H 2 2 185-188 7 Cu 4-ci 1 WHAT 2 3 “ ⁿ⁰ 2 4-Cl 1 2 185-190 8 Cu 4-Cl 1 what 2 H 2-OH 0 2 93- 96 9 Cu 4-Cl 1 what 2 2-C 3 H ₇ -O-CO H 1 2 130-135 10 Cu 4-Cl 1 what 2 2-C1 H 1 2 113-116 11 Cu 4-Cl 1 what 2 4-Cl H 1 2 128-130 12 Mg 4-Cl 1 what 1 2,4-Cl H 2 2 13 Sn 2,4-Cl 2 what 2 2,4-Cl H 2 2 74-75 14 Mn 4-Cl 1 what 1 4-Cl H 1 1 124-127 15 Dec Cu 4-Cl 1 what 2 3,5-NO ₂ 4-Cl 2. 2 165-170 16. Mn 4-Br 1 what 2 3,5- ^ NO, 4-Cl 2 2 188-189 17 Mn 4-Br 1 C (OH) H 3 4-Cl H 1 2 176-179 18 Zn 2,4-Cl 2 WHAT 2 2-C1 H 1 2 108 19 Dec Cu 4-Cl 1 WHAT 2 4-F H 1 2 194-197 20 May Cu H 0 C (OH) H 4 2-C1 H 1 2 108-110

Ex

Example 21% highly disperse silicic acid,% kaolin

Dispersible powder containing 25% active. Composition: 25% of the active ingredient of Example 5, lignin sulphonate, 1% of alcohols, for example 22% highly disperse silicic acid. ,

Dispersible powder containing 50% effective

Ingredients: 50% of the active ingredient of Example 1, aigisuafoiate, 2% of methyl lauride, and 32% diatomaceous earth.

said a d 23

Mash containing 25% active ingredient

Composition: 25% of the active compound according to the example, 0.5% dye, ^63.5 % kaolin.

16, 10% lignin sulphonate, 1% alkylnaphthalene, and d

Suspension

Ingredients:

caseinate containing 10% active ingredient 10% active ingredient solution.

according to the example

14.5% lignisulfoate, 0.5% dye and 84.5% magnesium; and d

Mash containing 20% active Ingredients: 20% active ingredient 69.5% dimethylsulfoxide.

substances according to the invention

8, 0.5% dye, Л1.0% isopropylpropyl, and d 26

ΈmulgoovSelný konccenrát with Composition: char ^ ter ^ lddonu and 40 containing 10% of active substance according to Example 12, 5%%% active ingredient mofn / di / - ^(t hy fxyl Aayla ^l) TS ^T tru к е ^ !! ^ xylene.

organic sulfonate nonionic frt fsffrečn ^{f h} f ^{e, 40%} of N-meehy ^y 1 - pyyroP plots and

Powder

Ingredients:

oil and 70% kaolin.

25% active ingredient% 20% active ingredient, 2% dye, 3% purified mineral

Example

Dust with Ingredients:

containing 1% active ingredient% active ingredient of Example 13, 10% kaolin and 89% mmst.

Product example N-alkylnaphthaleneSuspension concentrate containing 40% active ingredient

Ingredients: 40% of the active ingredient of Example 6, 3% of the condensation sulfonate with formaldehyde, 4% of anionic and nonionic surfactants, 1% of antioxidant, 0.1% of anionic polysaccharide, 5.0% of ethylenilyl and 46 , 9% water.

Example '30

Oily suspension concentrate containing 25% active substance

Composition: 25% of the active ingredient of Example 5, 6% of a polyethylene glycol ether of an alpha alcohol, 34% of water and 35% of paraffin oil.

Example 31

Suppression of palms

The wheat type is sown in the usual mixed soil in pots.

At least 10 rossiins are grown in each pot. After reaching the second or fourth to sixth leaf stage, the plants are shed.

A spray slurry was prepared from the composition of Example 21. With conventional spray containers (for example of the Tee Jet TG or TK type) arranged on the frame of a conventional conventional field sprayer, the plants are sprayed with a preparation of the specified active substance content.

Twenty-four hours after treatment, the plants were inoculated with powdery mildew of Erysiphe graminis fs tritici. The pot was in a hurry to stand 5-7 ^hours in a glass soubězíe for te ^p lo ^{most 20} ° C.

The attack is evaluated 12-14 days after treatment according Hinínera (Hi.njfnejr K. Békési P: ° rszágos Faltl ^to ITER NRN ^{l to} [^ country's experiments-ICH] 113, 1971, Budd ^^ t.

The active substance, its concentration and the results obtained are given in Table I.

Table I

Suppression of E .alpha

Active substance

Example 16

Percent suppression

10 µg / ml 0.5 µg / d

60

Example 7

Example 5

Example 10

Example 11

Active Substance IV

29

83 97 78 81 76 90 80 82

(known)

He said a 32

The systemic effect of prooi falls wheat

In order to determine the tympanic effect, the soil from the plants is covered with a prosthesis containing the active substance treated similarly as in Example 31. The concentration of the active substance in the formulation is given per unit volume of soil. The watering is carried out in accordance with the rossiin requirements.

The active substance, its concentration and the results obtained are given in Table II.

Table II

Systemic effect against powdery mildew of wheat

Active substance

Percentage attack г ^ О / ид / ш! ^1, 2 ^ ^5y m u / ml ^{0 625 /} u ^{g /} ml ⁺

Example 6

5.3

3.9 ab ⁺ ++

10.5

3,5 bcl

15.0 + 2.2 d

Compound V (known)

2.3

1.7

4,5

3,3 ab

8.3 + 4.1 abcd

Compound VI ^{(Zn ++} a)

26.2

5.7

36.5

7.6

33.8 + 7.3 f

Konnrola

56.8 ^SzD 5%

6.82 soil ++ +++ concentration V / µg per ml volume tenfold concentration (2.50, Duncan test (Duncan Multiple Range will not drive letters with probability P = 95% no resolution)

12.5 and 6.25 (µg / ml)

Tees), ie. data with themselves

Example 33

Therapeutic effect against wheat padU

To test the therapeutic effect, the procedure is analogous to that described in Example 31, except that the plants are treated with the drug-containing composition 2 days after challenge and evaluated 14 days after seeding.

The active substance, its concentration and the results obtained are given in Table III.

hive

а III

Therapeutic effect

Active substance

Percentage attack

Concentration of the active substance in [mu] g / ml

25 12.5

Example 6 5,3 + 1, Compound V (known) 13.8 + 5, Compound VI ^{(Zn +} a) 50.3 + 5

3 a 10.3 + 1.7 ab 22.3 + 5.0 d 7 bcd 18.8 + 1.5 CD 19.0 + 3.4 CD , 2 e 54.0 8.5 E 50.8 + 2.5 E

Konnrola ^SzD 5%

51.0 + 3.4 e

7.29 tenfold concentration (500, 250 and 125 / тд / ml).

in

Example 34

Effect against powdery mildew on cucumbers

Cucumbers of Kecskeméti botermo type are sown in mixed garden soil in pots for plant growing. The two plants per pot were grown to the fourth leaf stage or the sixth leaf stage, respectively. The rootlins are sprayed with the active substance in the form of a spray slurry using a spray gun up to the humid atmosphere accompanied by droplets.

After 24 hours, the plants are infected with a spore suspension of powdery mildew of Spheaarotheca fuiginea containing 10 ⁵ spores per milllitre. The pots are kept in a greenhouse at 24 ^° C. Infestation is evaluated after 14 days according to Spencer (Crop Protection Agents - Thhir Biological Evvauation, Ed.

N. R. McFaalene, Academic Press, pp. 455 et seq., 1977).

. The active substance, its concentration and the results obtained are given in Table IV.

Table IV

Systemic effect on cucumbers

Active substance Attack, in percent

Active substance concentration in µg / ml 50 25 12.5

Example 6 4.2 + 2.4 and 14.0 + 7.0 bcd 22.0 + 6.0 de Compound V 11.0 + 7.6 ab 12.5 + 3.7 abc 22.3 + 4.4 de (known) Compound VI (known ⁺ ) 60.5 + 3.3 F 58.0 + 9.3 F 53.5 + 3.4 F

Koonrola 88.0 + 1.6

SzD _5% 8.09 + tenfold concentration (500, 250 and 125 µg / ml).

Example 35

Systemic effect against powdery mildew on cucumbers during soil treatment

The systemic effect of soil treatment is performed similar to that described in Example 32. The results are shown in Table V.

Table V

Active substance

Example 6

Compound V (known)

Percentage attacked

Treatment of the active compound in µg / ml

2.50 1.25 0.625

3.8 + 3.3 and 15.3 + 8.1 cde 22.3 + 4.3ef

0.0 +0.0 and 2.5+ 3.3 ab 18.5 + 8.7 de i

continuation of Table

Active substance Percentage attack

Active ingredient concentration

2,50 1,250,625

Compound VI.

(Zn ^and has ⁺⁾ 76.8 ⁺ 3.8 71.0 ± GH 74.8 + 6.5 g 5.7 g

Control 84.0 + 4.2

SzD ₅ % 7.72 + tenfold concentration (25.0, 12.5 and 6.25 µg / ml).

Example 36

Suppressing powdery mildew in barley

Viktoria barley is sown in the mixed soil in pots for plant growing. IN

At least 10 plants are grown in each pot until the fourth to sixth leaf stage.

The procedure is as described in Example 31.

The results are shown in Table VI.

Ta b u 1 k and VI

Contact effect for barley

Active substance Percentage attack

Concetration of the active ingredient in µm / ml

25 12.5

Example 6

Compound V (known)

5.0 + 2.0 and 6.0 + 2.0 a

8.7 + 1.5 and 8.3 + 3.3 a

11.7 + 3.2 a

13.0 + 1.0 a

Compound VI ^{(Zn + M)}

23.3 + 13.3 b 27.3 + 4.7 b

27.7 + 2.1 p

^οπ ^^ Ιι ^Sz D ⁵ %

56.7 + 2.3

6.91 + tenfold concentration (500, 250 and 125 µl / ml).

Example 37

Treatment of soil prooi padia barley

The results obtained in soil treatment are given in Table VI.

Table VII

Soil treatment in barley.

Active substance Percentage attack

Concentration of the active ingredient in µg / ml

2.50 1.25 0.625

Example 6 3.3 + 2.3 ab 10.3 + 5.9 Bc 9.3 + 2.1 Bc Compound IN 0.7 + 0.6 and 2.3 and 1.5 ab 9.3 + 2.1 Bc (known) Compound VI 25.7 + 3.1 d 23.7 + 9.1 and 22.0 + 4.6 d

(known ⁺ )

Control 51.0 + 8.2

SzDg% ₍ 7.06 + tenfold concentration (25.0, 12.5 and 6.25 µg / ml), respectively).

Example 38

Suppressing wheat powdery mildew in the open field

In the open field, winter wheat of the Mv-4 type is sown by conventional agrotechnical methods.

At the end of autumn or early winter, the field is contaminated by Erysiphe graminis f.s. tritici. In the spring, parcels of 3.5 x 4 m, which do not lie in the inner part of the field, are determined. At the same time, the plot should be adjacent to each plot without treatment. The parcels are treated with conventional plant protection technology. '

The challenge is determined on the 21st day after the last Hinfner treatment.

The active substance, its concentration and the results obtained are given in Table VIII.

Table Fairies

Free field experiments

Active substance Percent attack Concentration of active substance in kg / ha 0.75 0.375 Example 6 23.00 (1.41); 31.50 (3.54) ab Example 5 36.50 (6.36) abc 46.00 (4.24) cd Compound V 33.50 (3.54) abc 46.00 (4.24) cd (known) Control 60,00 (1.41) d

The known compounds of formulas IV, V and VI, which were used as active substances in Examples 31 to 38, have the following chemical formulas;

(IV)

(VI)

The advantages of the present invention may be summarized as follows:

- the invention makes it possible to reduce the amount of traazole compound used, which is of great importance for environmental protection,

- lower cost of the active substance may be taken into account economically,

the active compounds according to the invention are easy to obtain and ingest.

Claims (1)

A fungicidal composition comprising as active ingredient at least one traazol metal complex of the general formula I (I) wherein: Me X Q represents represents represents me <d atom, zinc, manganese, tin or magnesium, a halogen group of the formula CO or formula -CH (OH) means ^N _ ₄ alkoxy-arbonylovou to-pin-group of ^even troskžpiož or ^ 1 ^ - γ represents a hydrogen atom, a halogen atom or a Uyirtxy group, U.S is zero, 1 or 2, sludge are 1, 2, 3 or 4; and p means an integer between zero and 6. 2. Method 3. A method according to claim 1 wherein: The triazole derivative of formula (II) is reacted CHo I ³ O-CH-QI (II) wherein X, Q and n are as defined above, with a metal salt of formula III (III) 1 2 wherein Me, X, Y, m, 1 ap mail abovementioned meaning, at temperatures ^y mmei 5 and 50 ° ^C, especially at temperatures ^{s 20 and 25} ° C in the present ^ and water or an organic solvent such as alcohol.