HU184522B - Fungicide composition containing triazole derivatives and process for preparing the active substance - Google Patents

Abstract

The fungicidal compositions of the present invention are: wherein Z is optionally substituted phenyl; - R 1 is cyano or C 1-12 alkyl; R2 is hydrogen, C1-C8 alkyl or allyl; or - R1 and R2 together with the carbon atom to which they are attached form a cyclopentyl group; and - Q 1 - (1,2,4-triazolyl) - or 4- (1,2,4-triazolyl) -. The present invention also provides a process for the preparation of a triazole derivative of formula (IX) wherein Z is optionally substituted phenyl; - R 1 is cyano or C 1-12 alkyl; R2 is hydrogen, C1-C8 alkyl or allyl; or - R 1 and R 2 together with the carbon atom to which they are attached form a cyclopentyl group. The process involves reacting a compound of formula (V) with a compound of formula (VI) in an inert solvent in the presence of a catalyst. -1-

Description

FIELD OF THE INVENTION The present invention relates to fungicidal compositions containing as active ingredient triazole derivatives, optionally in an agriculturally acceptable enantiomorphic form, or in the form of an acid addition salt or a metal complex, wherein Z is optionally substituted with one or two halogen atoms or phenyl substituted by phenoxy;

- R ¹ is cyano or C 1 -C 12 alkyl;

- R ² is hydrogen, C 1-8 alkyl or allyl; or - together with R ¹ and R ² together with the carbon to which they are attached is cyclopentyl; and Q is 1- (1,2,4-triazolyl) or 4- (1,2,4-triazolyl).

The present invention also relates to a process for the preparation of the compounds used as an active ingredient.

A review of Chemical Abstracte 76, 113,224p discloses 4H-triazoles which may be substituted by alkyl, CA 81.91539 u [(arylnitro) ethyl] azoles, and CA 87 53317 m [(0-phenyl). 0-halo) ethyl] tyrazoles. U.S. Patent No. 3,769,411 describes 4 - [(alkyl optionally substituted by halogen, alkoxy, hydroxy or nitro) triazoles.

The acids which may be used in the preparation of the acid addition salts of the present invention include hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, iodine hydrogen, hydrofluoric acid, perchloric acid, p-toluenesulfonic acid, methanesulfonic acid, acetic acid, citric acid, malic acid, malic acid , oxalic acid, fumaric acid, phthalic acid.

The metal salt complex of formula (III) may also be used as an active ingredient in the compositions of the present invention. In the formula (III):

Z, R ¹ , R ² and Q have the same meaning as in general formula (I); , - M represents II / A, I / B of the periodic table,

A group II / B, VI / B, VII / B or VIII cation;

X is an anion with the same charge number as cation M.

Examples of M are magnesium, manganese, copper, nickel, zinc, iron, cobalt, calcium, tin, cadmium, mercury, chromium, lead or barium.

X is, for example, chloride, iodide, bromide, fluoride, sulfate, bisulfate, perchlorate, nitrate, nitrite, phosphate, carbonate, bicarbonate, acetate, cephrate, oxalate, tartrate , malate, maleate, fumarate, ρ-toluenesulfonate, methanesulfonate, (mono) or (di) (C 1 -C 14 alkyl) dithiocarbamate or C 14 alkylene bis-dithiocarbamate.

For example, the following compounds may be used as active ingredients in the compositions of the invention:

- [O- (2,4-dibromophenyl) hexyl] -1,2,4-triazole,

- [O- (4-phenoxyphenyl) hexyl] -1- (2,4-triazole,

4- [O- (3-iodo-phenyl) -decyl] -1,2,4-triazole,

- (O- (2,6-dichlorophenyl) pentyl] -1- (2,4-triazole,

4- (0- (3,5-diethylphenyl) butan-2-yl] -1,4-triazole,

4- [O- (4-iodo-phenyl) -undecyl] -1,2,4-triazole,

- [O- (2-methyl-4-chlorophenyl) dodecyl] -1,2,4-triazole,

4- (O- (3,4-dichlorophenyl) octyl] -1,2,4-triazole,

- (O- (2,3-difluorophenyl) propyl] -1- (2,4-triazole,

4- (O- (2,5-diethylphenyl) tetradecyl] -1- (2,4-triazole, 1- [O- (cyano-O- (2,4-dibromo-phenyl) hexyl)] -1,2,4-triazole,

4- [O-cyano-O- (3-iodo-phenyl) -decyl] -1,2,4-triazole,

- [O-cyano-O- (2,6-dichlorophenyl) pentyl] -1- (2,4-triazole,

4- [0-cyano-O- (3,5-diethylphenyl) butan-2-yl] g-1,2,4-triazole, 4- [O-cyano-O- (4- iodophenyl) -undecyl] -1,2,4-triazole,

- [0-cyano-0- (4-tolyl) hexyl] -1,2,4-triazole,

4- [O-cyano-O- (2,4-dichlorophenyl) -O-cyclopentylethyl] -1- (2,4-tri-azole,

4- [O-cyano-O- (3,4-dichlorophenyl) octyl] -1,2,4-triazole,

- [O-cyano-O- (2,3-difluorophenyl) propyl] -1,2,4-triazole, 4- [O-cyano-O- (2,5-diethylphenyl) tetradecyl] -1,2,4-triazole.

Also agriculturally acceptable acid addition salts and metal salt complexes of these compounds can be used as active ingredients.

The 1- and 4-substituted triazoles can be prepared in a manner known per se. A preferred process for preparing the 1-substituted-1,2,4-triazoles of the present invention is illustrated in Scheme A. In the reaction scheme:

- Z, R ¹ , R ² , and Q are as defined for formula (I);

- Y represents a halogen atom, an alkylsulfonate, an arylsulfonate or a 1- (1,2,4-triazolyl) metal salt,

Q is preferably a sodium or potassium salt.

The reaction, with or without a suitable solvent (benzene, toluene, xylene, N, N-dimethylformamide, dimethylsulfoxide and the like), is carried out at a temperature of about 0 ° C to about 150 ° C, preferably at reflux temperature.

When the starting material of formula (IV) is reacted with the 1H-1,2,4-triazole free base at about 50-180 ° C instead of the metal salt, the 1-substituted and 4-substituted-1,2,4-triazoles mixture. These triazoles can be readily resolved by conventional chemical separation procedures such as extraction, chromatography or crystallization.

A preferred process for preparing the 4-substituted-triazole active compounds of the present invention is illustrated in Scheme B below. In the general formula, Z, R ¹ and R ² have the same meaning as in the compound of formula (I).

This reaction is suitably carried out in an inert solvent such as benzene, toluene or xylene, at a temperature of about 0 ° C to about 150 ° C, in the presence or absence of a suitable catalyst (e.g. Both reagents, i.e. compounds of formula (V) or (VI), may be used in excess.

The starting materials of formula (IV) may be prepared by known procedures.

The starting material of formula (V) is prepared by reacting the appropriate starting material of formula (IV), e.g. Y, chloride or bromide, with or without a suitable solvent (e.g., diethyl ether, tetrahydrofuran, methanol) at -40 ° C. and at a temperature between 100 ° C and 100 ° C.

The acid addition salts of 1- and 4-substituted-1,2,4-triazoles in the compositions of the present invention may be prepared by methods known to those skilled in the art, for example, the 1- or 4-substituted-1,2,4-triazole of formula I dissolved in a suitable solvent such as diethyl ether, tetra-21

184,522 in hydrofuran, ethyl alcohol, methanol and then equivalent or excess mineral or organic acids. The mixture is then cooled or evaporated, and the salt thus obtained is used or, if not yet suitable, recrystallized from a suitable solvent or solvent mixture and then used.

The metal salt complexes of the 1- and 4-substituted-1,2,4-triazoles described above can be prepared as follows: a suitable solvent for the 1- or 4-substituted-1,2,4-triazole of formula (I) to the solution is added dropwise with stirring a stoichiometric amount of the metal salt solution. The reaction mixture is stirred briefly and the solvent is evaporated under reduced pressure to give the 1- or 4-substituted-1,2,4-triazole metal salt complex of formula (III).

Any polar solvent such as water, methanol, ethyl alcohol, isopropyl alcohol or ethylene glycol can be used in these operations and some aprotic dipolar solvents such as dimethylsulfoxide, acetonitrile, dimethylformamide, nitromethane or acetone. Preferred metal salt cations include calcium, magnesium, manganese, copper, nickel, zinc, iron, cobalt, tin, cadmium, mercury, chromium, lead, barium.

Examples of metal salt formation include chloride, bromide, iodide, sulfate, bisulfate, phosphate, nitrate, perchlorate, carbonate, bicarbonate, hydrogen sulfide, hydroxide, acetate, oxalate, malate, , dtratanion.

The thiazole derivatives of the present invention contain an asymmetric carbon atom, except for those wherein R ¹ and R ^{2 are} both hydrogen, so that they are prepared in a racemic form. The d and 1 enantiomorphic forms in the racemate can be separated by known procedures such as fractional crystallization with d-tartaric acid, 1-tartaric acid or 1-kinosa, and the mixture is made basic and the d1 or 1 enantiomorphic free base is extracted by extraction.

The following describes the preparation of the active compounds of the compositions of the invention.

Example 1

Preparation of 4- [2- (2,4-dichlorophemyl) hexyl] -1,2,4-triazole

A. Preparation of 2- (2,4-dichlorophenyl) hexylamine

To a suspension of 0.9 g (-, 24 moles) of lithium aluminum hydride in 200 ml of anhydrous ether was added 57 g (0.24 moles) of α-n-butyl-2,4-dichlorobenzyl cyanide at 10 ° C. The reaction mixture was stirred at room temperature for 30 minutes and at 35 ° C for 12 hours. The excess lithium aluminum hydride was then quenched by the addition of 50 mL of saturated ammonium chloride solution and 300 mL of 20% HCl at 0 ° C. The acidic aqueous phase was separated and extracted with ether. The combined ether extracts were washed with water and dried over magnesium sulfate. Evaporation of the ether in vacuo gave 63 g of a yellow solid. This solid was dissolved in 20% sodium hydroxide and extracted with ether. The combined ethereal extracts were dried over MgSO4. After evaporation of the solvent, vacuum distillation of 48 g of oil (101-104 ° C / 0.1 mm Hg) gave 38.3 g of pure product.

B. Preparation of 4- [2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazole g (0.04 mol) 2- (2,4-dichlorophenyl) hexylamine A mixture of 7 g (0.04 mol) of Ν, Ν-dimethylformamide azine and -0.5 gp-toluenesulfonic acid in 100 ml of anhydrous toluene was refluxed for 16 hours. After evaporation of the solvent, 15 g of a white solid remain which can be increased by recrystallization from benzene to give 7.5 g of pure product.

NMR (CDCl ₃ ) δ: 0.8 - 2.0 (complex multiplets, 9H),

3.8 (m, 1H), 4.3 (d, 2H), 7.3 (m, 3H), 8.0 (s, 2H).

Example 2 1- [2- (2,4-Dichlorophenyl) hexyl] -1,2,4-triazole and 4- [2- (2,4-Dichlorophenyl) hexyl] -1,2 Preparation of 4-triazole

A. Preparation of 2- (2,4-dichlorophenyl) hexyl methanesulfonate

See Example 4 for the preparation of the compound.

B. 1- [2- (2,4-Dichlorophenyl) hexyl] -1,2,4-triazole and 4- [2- (2,4-Dichlorophenyl) hexyl] -1,2, Preparation of 4-Triazole A mixture of g (0.025 mol) of 2- (2,4-dichlorophenyl) hexyl methanesulfonate and 6 g (0.087 mol) of 1H-1,2,4-triazole was heated to 120 ° C. hours at this temperature. The reaction mixture was then poured into water and extracted with ether. The combined ether extracts were washed with water and dried over MgSO ₄ . After filtration of the desiccant, the filtrate was added dropwise to the filtrate. nitric acid is added until no precipitation is observed. The solvent is then decanted off, the residue is washed with ether and neutralized with dilute NH ₄ OH. The product was 3 g of an oil which was determined by layer chromatography and NMR analysis to give 1- [2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazole and 4- [2- (2) , 4-dichlorophenyl) hexyl] -1,2,4-triazole 2: 1.

NMR (CDCl 3), δ: 0.7-2.0 (m, 9H), 3.64.0 (m, 1H),

4.24.9 (m, 2H), 7.0-73 (m, 3H), and the singlets are integrated at 7.3, Ifi, and 8.0 at 2H.

Example 3 Preparation of 1- [2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazole

Neutralization of the nitrate salt of the compound described in Example 4 with 10% ammonium hydroxide gave the 1- (2- (2,4-dichlorophenyl) hexyl) -1,2,4-triazole free base.

NMR (CDCl 3), δ: 0.7-2.0 (complex multiplets, 9H),

3.9 (m, 1H), 4.4 (d, 2H), 7.0-7.5 (m, 3H),

7.8 (s, 1H), 7.95 (s, 1H).

Example 4 Preparation of 1- [2- (2,4-dichlorophenyl) hexyl} -1,2,4-triazolium mtrate

A. Preparation of 2- (2,4-dichlorophenyl) hexyl methanesulfonate

24.7 g (0.1 mol) of 2- (2,4-dichlorophenyl) hexan-1-ol and 3

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To a mixture of methanesulfonyl chloride (13.8 g, 0.12 mol) in benzene (200 ml) was slowly added triethylamine (14.2 g, 0.14 mol) at 10 ° C. The reaction mixture is stirred and allowed to stand for more than half an hour until it reaches room temperature, and the resulting slurry is refluxed for half an hour, cooled and poured into water. The organic phase is washed first with dilute hydrochloric acid, then with water and finally with dilute sodium bicarbonate solution. The crude product remaining after drying over anhydrous MgSO ₄ and removal of benzene weighed 31.8 g (98%). The product is analyzed by infrared spectroscopy and NMR spectroscopy, and its purity is determined by layer chromatography.

B. Preparation of 1- \ 2- (2,4-dichlorophenyl) hexyl} -1,2,4-triazolium nitrate

To a solution of sodium 1,2,4-triazole (2.2 g, 0.032 mol) in 1H-1,2,4-triazole and 1.3 g (0.032 mol) in 25 ml of dimethylsulfoxide was added a solution of (03 mol) of a mixture of 2- (2,4-dichlorophenyl) hexyl methanesulfonate in 10 mL of dimethyl sulfoxide was added dropwise at 100 ° C. After 1 hour at 100 ° C, the reaction mixture was poured into water and extracted with ether. The combined ether extracts were washed with water, dried majd'vízmentes MGS0 ₄ -one. After filtration of the desiccant, the filtrate was cc. nitric acid is added until no precipitation is observed. The white precipitate (7.5 g) was filtered off, which was the nitric acid salt of the desired product.

NMR (DMSO), δ: 0.7-2.0 (complex multiplets, 9H), 3.9 (m, 1H), 4.7 (d, 2H), 7.5 (m, 3H), δ Δ (s, 1H), 9.0 (s, 1H), 9.3 (s, 1H).

Example 7 Preparation of 1- [2- (2,4-Dimethylphenyl) -hexU} -1,2,4-triazole zinc chloride complex of 3.0 g (0.0116 mole) of 1- [2- Zinc chloride (0.71 g, 0.0052 mol) was added to 2,4-dimethylphenyl) hexyl] -1,2,4-triazole and the mixture was stirred for 15 minutes. After removal of methanol, 3.7 g remain. This material was triturated with hexane, filtered and dried to give 3.3 g (71.9%) of product, m.p. 85-86 ° C.

Example 10

Preparation of 1- (2-phenyl-tetradepyl) -1,2,4-triazole hydrochloride for 6.6 g (0.09614 mol) in 1H-1,2,4-triazole (6.0 g) in DMSO Particulate sodium hydroxide (0948 mol) was added and the resulting mixture was heated and stirred until a clear solution was obtained. To this was added 25 ml of toluene and the reaction mixture was refluxed. The resulting water was removed by azeotropic distillation, then toluene removed and the DMSO solution cooled. To this solution was added 35.3 g (0.0958 mole) of 2-phenyltetradecyl methanesulfonate, which was prepared in a conventional manner. The reaction mixture was then heated to 130 ° C, held at this temperature for 20 hours, and then cooled. To the resulting solution was added water (250 mL), and the separated organic material was extracted with ether (2 x 200 mL). The extract was dried over anhydrous magnesium sulfate and then treated with hydrogen chloride gas. The precipitated solid salt was collected by filtration, washed with ether and dried to give 16.9 g (46.7%) of crude hydrochloride m.p. 50-53 ° C. Recrystallization of 5 g of the hydrochloride salt from ether / acetone gives 3.6 g of 1- (2-phenyltetraderyl) -1,2,4-triazolium chloride, m.p. 82-88 ° C.

Example 11 Preparation of 1- (2-phenyltetradecyl) -1,2,4-triazole

11.7 g of the crude hydrochloride salt obtained according to the procedure of Example 10 are taken up in 200 ml of water and 4.0 g (0.05 mol) of 50% sodium hydroxide are added. After stirring for 15 minutes, the organic solution was extracted with ether (2 x 200 mL). The combined ether extracts were washed with water (2 x 50 mL), dried over anhydrous magnesium sulfate, and concentrated. 8.3 g (78.5%) of an oil are obtained.

Example 12 Preparation of 1- [1,10-tetramethylene-F (2,4-dichlorophenyl) ethyl] -1,2,4-triazolium chloride

A. Preparation of α-tetramethylene-2- (2,4-dichlorophenyl) ethyl methanesulfonate

1. Preparation of aa-tetramethylene-2,4-dichlorobenzyl cyanide

A 500 ml three neck flask was charged with 200 ml of 25% sodium hydroxide solution and 4 g of tetraethylammonium bromide. To this suspension was added dropwise a solution of 33.5 g (0.2 mol) of 2,4-dichlorobenzyl cyanide and 43 g (0.2 mol) of 1,4-dibromobutane in 200 ml of methylene chloride under nitrogen pressure. added. The reaction mixture was refluxed for 1.5 hours, then poured into water and the resulting phases were separated. The aqueous phase is extracted with 100 ml of methylene chloride. The combined organic extracts were washed with water, saturated sodium chloride solution and dried over magnesium sulfate. After evaporation of the solvent, a light yellow oil remains. Vacuum distillation (130-140 ° C / 0.2 mm Hg) yields 30.4 g (63%) of the crude product which is identified by NMR.

2. Preparation of wx-tetramethylene-2,4-dichlorophenylacetic acid A mixture of g, 0.06 mol) of α, α-tetramethylene-2,4-dichlorobenzyldidane in 160 ml of 40% potassium hydroxide solution and 120 ml of ethyl acetate. of diethylene glycol was refluxed for 3 days. The reaction mixture was poured into water and extracted with ether. The aqueous phase was acidified with hydrochloric acid and extracted with ether. The cores of the combined ethereal extracts of the acidified solution were washed with water and saturated sodium chloride solution and dried over magnesium sulfate. After evaporation of the solvent, 12.4 g of crude product (acid) is recrystallized from hexane / benzene to give 8 g of pure product (m.p. 136-138 ° C).

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3. Preparation of 2,2-tetramethylene-2- (2,4-dichlorophenyl) ethyl alcohol To a suspension of lithium aluminum hydride (g, 0.08 mol) in anhydrous ether (300 ml), add dropwise 13 ml of ether under nitrogen pressure. (0.05 mol) arxetramethylene dichlorophenylacetic acid was added. The reaction mixture was then refluxed for one hour. The excess lithium aluminum hydride was carefully decomposed by adding 10% hydrochloric acid dropwise to the reaction mixture. The two phases are separated and the aqueous phase is extracted with ether. The combined ether extracts were washed with water and dried over magnesium sulfate. After evaporation of the solvent

9.8 g of product (alcohol) are obtained which is identified by NMR.

4. Preparation of 2,2-tetramethylene-2- (2,4-dichlorophenyl) ethyl methanesulfonate

To a mixture of 9.8 g (0.04 mol) of 2,2-tetramethylene-2- (2,4-dichlorophenyl) ethyl alcohol and 5 g (0.04 mol) of methanesulfonyl chloride in 30 ml of benzene is added dropwise Triethylamine (g, 0.05 mol) was added. The reaction mixture was stirred overnight and the precipitate was filtered off. The benzene solution was washed first with water, then with dilute hydrochloric acid and dried over magnesium sulfate. After evaporation of the solvent, 12 g of product are identified by NMR.

B. Preparation of 1- {p < tetramethylene-P- (2,4-dichlorophenyl) ethyl] -1,2,4-triazolium chloride in 0.65 g (0.009 mole) of 1H-1,2 in DMSO To the 4-triazole was added 0.37 g (0.009 mole) of particulate sodium hydroxide, and the mixture was stirred until heated to 60 DEG-90 DEG C. until complete dissolution. To this solution was added 25 mL of toluene and refluxed. The resulting water was removed from the mixture by azeotropic distillation, then toluene was removed and the DMSO solution was cooled to 115 ° C. To this solution, 3 g (0.009 mol) of 2,2-tetramethylene-2- (2,4-dichlorophenyl) ethyl methanesulfonate in 10 ml of DMSO was added dropwise. The temperature of the reaction mixture was then maintained at 115 ° C for 2 hours, and the reaction mixture was poured into 150 ml of water and extracted with ether. The combined ether extracts were washed with water and dried over magnesium sulfate. After removing the solvent

2.5 g of crude product are obtained. This material was dissolved in ether (200 mL) and bubbled with dry hydrogen chloride gas. The resulting precipitate was filtered, dried in vacuo to give 1.2 g of the expected product. 175-179 ° C.

Example 13 Preparation of 1- [2- (2-phenoxyphenyl) hexyl] -1,2,4-triazolium chloride

A. Preparation of 0-phenoxybenzyl chloride

A 1 liter flat bottomed flask with stirrer, condenser, thermometer and funnel was charged with 25 g (0.125 mol) of o-phenoxybenzyl alcohol and 250 ml of benzene. Thionyl chloride (18.0 g, 0.15 mol) was added dropwise at room temperature. The reaction mixture was then refluxed for 2 hours. After evaporation of the solvent in vacuo, 29 g of product remain.

B. Preparation of a-n-butyl-o-phenoxybenzyl cyanide

A three-necked, 300 ml flask with a stirrer, condenser, thermometer and funnel was charged with 50 ml of dimethyl sulfoxide and 7.4 g (0.15 mol) of sodium cyanide. 30 g (0.14 mol) of o-phenoxybenzyl chloride dissolved in 10 ml of dimethyl sulfoxide are added dropwise at room temperature and the reaction mixture is stirred for 1.5 hours. 13.5 g (0.14 mol) of butyl chloride and then 34.3 g (0.43 mol) of 50% sodium hydroxide solution are added dropwise to the reaction mixture. The reaction temperature was raised to 52 ° C and stirred for one hour, diluted with water (150 mL) and extracted with hexane. The combined hexane extracts were washed with water and dried over magnesium sulfate. After evaporation of the solvent, 32 g of product are obtained, which product can be further purified by vacuum distillation (spinning 137-142 ° C / 0.2 mm Hg).

C. Preparation of n-butyl 2- (o-phenoxyphenyl) hexanoate

A 500 mL round bottom flask was charged with 77.7 g (1 mol) of n-butyl alcohol, 36.5 g (0.14 mol) of α-n-butyl-o-phenoxybenzyl cyanide and 14.4 g (0.45 mol) of cc. we make sulfuric acid. The mixture was refluxed overnight. The reaction mixture was cooled, poured into water and extracted with toluene. The combined extracts were washed with water and dried over magnesium sulfate. After evaporation of the solvent, 50 g of product remain.

D. Preparation of 2- (o-phenoxylphenyl) hexan-1-ol

With a stirrer, a condenser fitted with a drying tube, 1.8 g (0.047 mol) of lithium aluminum hydride and 50 ml of anhydrous ether are placed in a 500 ml three-necked round-bottom flask equipped with a thermometer and a funnel. For this dense suspension, 50 ml of ether are present

N-Butyl 2- (o-phenoxyphenyl) hexanoate (20.7 g, 0.05 mol) was added dropwise at 10 ° C. The reaction mixture was stirred at room temperature for 2 hours, poured into ice water and acidified with dilute hydrochloric acid. The mixture was then extracted with ether and the combined ether extracts were washed with water and dried over magnesium sulfate. The solvent was evaporated to give 17.5 g of crude product, which was purified by vacuum distillation (138-145 ° C / 0.25 mm Hg) to give 16.1 g of pure product.

E. Preparation of 2- (o-phenoxyphenyl) hexyl methanesulfonate

15.6 g (0.06 mol) of 2- (o-phenoxyphenyl) hexan-1-ol and 7.9 g (0.07 mol) of methanesulfonyl chloride are suspended in a 500 ml round-bottom flask. . To this mixture was added dropwise 8.2 g (0.08 mol) of triethylamine at 10 ° C. The reaction mixture was stirred overnight at room temperature and then poured into 150 ml of 10% hydrochloric acid. The mixture was extracted with benzene and the combined benzene extracts were washed with water and dried over sodium sulfate. After evaporation of the solvent, 20 g of product remain.

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F. Preparation of 1- [2- (2-phenoxyphenyl) hexyl] -1,2,4-triazolium chloride: 2.0 g (0.03 mol) of 1H-2,2,4 in dimethyl sulfoxide per ml. To the triazole was added 1.2 g (0.03 mol) of particulate sodium hydroxide and the mixture was heated (60-90 ° C) until complete dissolution. To this solution was added xylene (37 mL) and the reaction mixture was refluxed. The resulting water was removed from the mixture by azeotropic distillation, then the xylene was removed and the dimethylsulfoxide solution was cooled to 115 ° C.

To the solution thus obtained, 10.0 g (0.29 mol) of 2- (o-phenoxyphenyl) hexyl methanesulfonate in 10 ml of dimethyl sulfoxide is added dropwise. The reaction mixture was heated to 125 ° C, kept at this temperature overnight, then poured into 150 ml of water and then extracted with ether. The combined ether extracts were washed with water and dried over sodium sulfate. Evaporation of the solvent gave 8.0 g of crude product. This material was redissolved in 200 mL of ether and bubbled with dry hydrogen chloride gas. The precipitated solid was filtered off and dried in vacuo to give 5.6 g of the desired product, m.p. 142-146 ° C.

Example 75

Preparation of 4- [2-dano-2- (2,4-dichlorophenyl) hexyl} -1,2,4-triazole g (0.036 mol) 2-cyano-2- (2,4-dichlorophenyl) A mixture of hexyl bromide and 10 g (0.145 mol) of 1H, 2,4-triazole was heated to 185 ° C and maintained at this temperature overnight. The reaction mixture was cooled, poured into water and extracted with ether. When the combined ether extracts are washed with water, a white precipitate separates from the ether phase. Filtration of this precipitate after drying in vacuo gave 1 g of a white solid, m.p. 46-49 ° C.

Based on layer chromatography and NMR analysis, this is 4- [2-cyano-2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazole.

NMR (CDCl ₃ ) δ 0.7-3.2 (complex multiplets, 9H), 5.0 (q, 2H), 7.2-7.8 (m, 3H), 8.15 (s, 2H) .

Example 16 1- [2-Cyano-2- (2,4-dichlorophenyl) hexyl} -1,2,4-triazolium nitrate and 4- [2-cyano-2- (2,4-dichloro) -phenyl) -hexyl] -1,2,4-triazolium nitrate

To the ethereal filtrate described in the previous experiment, drop by drop cc. nitric acid is added so that the solution is strongly acidic. The resulting white precipitate was triturated several times with ether / hexane and combined with filtration to give 2 g of product, m.p. 110-120 ° C. Layer chromatography and NMR analysis showed this material to be a 2: 1 mixture of 1- [2-cyano-2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazolium nitrate and 4- [ 2-cyano-2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazolium nitrate.

NMR (DMSO) δ: 0.6-3.0 (m, 9H), 5.1 (q, 2H), 7.3-7.8 6. m, 3H) 8.1, 8.7 and 9, At 2, singlets were integrated into 2H, 14.2 (s, 1H).

Example 17

- Preparation of [2-cyano-2- (2,4-dichlorophemyl) hexyl] -1,2,4-triazolium nitrate

Preparation of 2-cyano-2- (2,4-dichlorophenyl) hexyl bromide

Dissolve 1.0 mole of n-butyl bromide and 1.0 mole of 2,4-dichlorophenyl cyanide in 250 ml of methylene chloride and add 500 g of 25% by volume with 5.0 g of tetraethylammonium bromide. aqueous sodium hydroxide solution. The reaction mixture was heated to reflux for 3 hours under vigorous stirring to give the desired product in 90% yield. This 90% purity is indicated by layer chromatography and NMR spectroscopy. The cyanide was then mixed with 1.3 M methylene bromide and this mixture was added together with the tetraethylammonium bromide or benzyltriethylammonium chloride used as the catalyst to a 50% aqueous sodium hydroxide solution. The reaction mixture was refluxed for 3 hours (90 ° C), during which time 95% of the starting material was converted. In this reaction, there is always about 5% a-n-butyl-2,4-dichlorobenzyl cyanide which is unreactive.

B. Preparation of 1- [2-cyano-2- (2,4-dichlorophenyl) hexyl} -1,2,4-triazole

Sodium 1,2,4-triazole (3.2 g, 0.046 mole) prepared from 1H-1,2,4-triazole and 1.85 g (0.046 mole) of sodium hydroxide was dissolved in dimethyl sulfoxide and 25 ml of this solution were added. 2-dano-2- (2,4-dichlorophenyl) hexyl bromide was added dropwise at 110 ° C. The whole was stirred at 110 ° C for 1.5 hours. The reaction mixture was poured into water (400 mL) and extracted with ether. The combined ethereal extracts were washed with water and dried over magnesium sulfate. After filtration of the desiccant, the filtrate was added dropwise to the filtrate. nitric acid is added until no precipitation is detected. The filtered precipitate (8.0 g) was the desired salt of the nitric acid salt (RH 45.136).

NMR (DMSO) δ: 0.6-25 (complex multiplets, 9H), 5.2 (q, 2H), 7.5-7.9 (m, 3H), 8.3 (s, 1H),

8.7 (s, 1H), 14.7 (s, 1H).

Example 18

The free base is obtained by neutralizing the above nitrate salt with 10% ammonium hydroxide solution.

NMR (CDCl 3) δ 0.7-2.8 (complex multiplets, 9H), 5.0 (q, 2H), 7.1-7.6 (m, 3H). 7.9 (s, 1H), 8.0 (s, 1H).

Example 23

Preparation of 1- (2-cyano-2-phenylhexyl) -1,2,4-triazole zinc chloride complex

184,522

To a solution of 1- (2-cyano-2-phenylhexyl) -1,2,4-triazole (6.5 g, 0.0256 mol) in methanol (120 ml) was added zinc chloride (1.5 g, 0.0111 mol), and stir for 15 minutes. Removal of the methanol left 9.6 g of material which was taken up in warm ethyl alcohol from which the solid precipitated. This was isolated by filtration to give 5.9 g (59%) of product, m.p. 175-177 ° C.

Example 25 1

Preparation of 1- (2-cyano-2-decyl) -1,2,4-triazole from 5.3 g (0.07697 mol) of 1H-1,2,4-triazole and 3.1 ml of DMSO 30.0 g (0.0767 mol) of 7.0 g (0.07697 mol) of the 1H-1,2,4-triazole sodium salt prepared from sodium hydroxide (0.759 mol).

2-Cyano-2- (2,4-dichlorophenyl) -decyl bromide was added and the reaction mixture was stirred for 20 hours at 130 ° C. The mixture was cooled and mixed with 200 mL of water. The separated organic material was extracted with ether (2 x 100 mL) and the extract was washed with water (2 x 100 mL), dried over anhydrous magnesium sulfate and concentrated to give 24.0 g (82.5%) of crude product. This material is dissolved in ether and treated with hydrogen chloride gas until the litmus indicator indicates an acidic pH. The precipitated solid was collected by filtration to give 9.0 g (28.2%) of the hydrochloride salt, m.p. 125-131 ° C. 200 ml of water

To the hydrochloride salt (6.7 g, 0.0161 mole) was added 2.0 g (0.025 mole) of 50% NaOH and stirred. The organic soluble material was extracted with ether (2 x 200 mL), the extract was washed with water (2 x 50 mL), dried over anhydrous magnesium sulfate and concentrated. The product was obtained as an oil (4.9 g, 30.2%).

Tables ΙΑ, IB, IIA, IIB include the meanings, melting point values and elemental analysis values of some of the preferred compounds of Formulas I, VII, and VIII.

The serial number of the example

IA. Compounds of Formula I or Formula VII ZR ¹ R ² Q

First 2,4C12 ₂ -C ₆ H ₃ C ₄ H ₉ n H 4-triazolyl - Second 2,4C12 ₂ -C ₆ H ₃ C ₄ H ₉ n H 1- and 4-triazolyl - Third 2,4C12 ₂ -C ₆ H ₃ C ₄ H ₉ n H 1-triazolyl - 4th 2,4C12 ₂ -C ₆ H ₃ C ₄ H ₉ n H 1-triazolyl hno ₃ 5th 2.4 (CH ₃ ) ₂ -C ₆ H ₃ C ₄ H ₉ n H 1-triazolyl HC1 6th 2.4 (CH ₃ ) ₂ -C ₆ H ₃ C ₄ H ₉ n H 1-triazolyl - 7th 2.4 (CH ₃ ) ₂ -C ₆ H ₃ C ₄ H ₉ n H 1-triazolyl 1/2 ZnCl 8th 2,4,6- (CH ₃ ) ₃ -C ₆ H ₂ ch ₃ H 1-triazolyl HC1 9th 2,4,6- (CH ₃ ) ₃ -C ₆ H ₂ ch ₃ H 1-triazolyl - 10th c ₆ h ₅ C ₁₂ H ₂ s H 1-triazolyl HC1 11th c ₆ h ₅ C1 2 H ₂ s H 1-triazolyl - 12th 2,4C12 ₂ -C ₆ H ₃ rHR ² = <CH ₂ ) 4 -C H 1-triazolyl HC1 13th 2-C ₆ H _s OC ₆ H ₄ C4 H9 π H 1-triazolyl HC1 14 3-C ₆ H ₅ OC ₆ H ₄ H 1-triazolyl hno ₃

IB. Compounds of formula I (wherein R ¹ = -CN) and compounds of formula VIII are shown in Table III

The serial number of the example Z R ² Q Y 15th 2,4-Cl ₂ -C ₆ H ₃ C4 H9 4-triazolyl _ 16th 2,4-Cl ₂ -C ₆ H ₃ C4 Η9Π 1- and 4-triazolyl ΗΝΟ3 17th 2,4-Cl ₂ -C ₆ H ₃ C4 Η9Π 1-triazolyl HN03 18th 2,4-Cl ₂ -C ₆ H ₃ C ₄ H ₉ n 1-triazolyl - 19th 4-Cl-C ₆ H 4 ch ₃ 1-triazolyl - 20th 4-Cl-C ₆ H 4 ch ₃ 1-triazolyl hno ₃ 21st c ₆ h ₅ C ₄ H ₉ n 1-triazolyl HC1 22nd c ₆ h _s C4H9 Π 1-triazolyl - 23rd c ₆ h ₅ C4H9I1 1-triazolyl l / 2ZnCl ₂ 24th 2,4-Cl ₂ -C ₆ H ₃ CeH 7 1-triazolyl HC1 25th 2,4-Cl ₂ -C ₆ H ₃ c _{6h 17} 1-triazolyl - 26th 2,4-Cl ₂ -C ₆ H ₃ ch ₂ ch = ch ₂ 1-triazolyl -

184,522 ₂

IIA. spreadsheet

Elemental analysis: calculated value (found value)

Example Melting point C H Cl NO or Zn sequence number C °

First 110-113 56.39 (56.55) 5.75 (5.99) 23.78 (23.38) 14.09 (14.05) Second oil 56.39 (56.11) 5.75 (5.81) 23.78 (23.89) 14.09 (12.70) Third oil 56.39 (56.19) 5.75 (5.87) 23.78 (23.95) 14.09 (13.69) 4th 108-110 46.55 (46.38) 5.02 (5.81) 19.64 (19.67) 15.51 (1522) 1329 (13.39) 5th 145-151 65.40 (65.66) 8.23 (8.37) 12.07 (11.76) 14.30 (14.47) 6th oil 74.67 (74.51) 9.00 (9.19) _ 16.33 (16.49) 7th 85-86 59.03 (58.72) 7.12 (7.14) 10.89 (10.56) 12.09 (13.16) 10.04 (10.47) 8th 180-187 63.26 (62.75) 7.59 (7.42) 13.34 (13.16) 15.81 (15.90) 9th oil 73.32 (72.00) 8.35 (8.05) _ 18.33 (18.33) 10th 82-88 69.90 (69.34) 9.60 (9.52) 9.38 (9.83) 11.12 (10.89) 11th oil 77.37 (77.32) 10.33 (10.37) - 12,30 (12.06) 12th 175-179 50.55 (50.19) 4.85 (4.83) 31.97 (29.20) 12.63 (12.68) 13th 142-146 67.12 (6723) 6.76 (6.79) 9.91 (10.11) 11.74 (12.07) 4.47 (5.04) 14th 121-124 62.49 (61.11) 6.29 (6.30) 14.57 (14.30) 16.65 (17.28)

184,522

IIB. spreadsheet Elemental analysis: calculated value (found value) The serial number of the example melting point ° C C H cl N O or Zn

15th 46-49 55.74 (55.40) 4.99 (5.12) 21.94 (21.82) 17.33 (17.18) 16th 110-120 46,65 (46.41) 4.44 (4.30) 18.36 (18.55) 18.13 (18.36) 12.43 (12.77) 17th 156-158 46,65 (46.30) 4.41 (4.61) 18.36 (18.50) 18.13 (18.27) 12.43 (12.54) 18th oil 55.74 (55.91) 4.99 (5.09) 2194 (22.07) 17.33 (17.21) 19th 114-116 58.43 (57.40) 4.49 (5.03) 14.37 (13.37) 22.71 (19.48) 20th 163 46.54 3.90 11.45 22.61 15.50 (Dec) (47.28) (3.90) (11.50) (21.97) (16.00) 21st 162-165 61.95 (61.10) 6.59 (6.35) 12.19 (10.49) 19,27 (17.91) 22nd oil 70 34 (71.36) 7.13 (7.19) - 22.03 (20.82) 23rd 175-177 55.87 (56.10) 5.60 (5.70) 10.99 (12.05) 17.37 (17.01) 10.13 (9.04) 24th 125-131 54.88 (54.80) 6.60 (5.95) 25.58 (24.77) 13.48 (13.76) 25th oil 60.16 (56.97) 6.37 (6.48) 18.70 (17.93) 14.77 (14.25) 26th 88-90 54.74 (54.97) 3.94 (3.97) 23.08 (22.85) 18.24 (18.59)

The 1- and 4-substituted-1,2,4-triazoles, enantiomorphs, acid addition salts and metal salt complexes used in the compositions of the present invention are broad-spectrum fungicides which exhibit high activity against various fungal pathogens, such as barley plants. fungus (Helminthosporium teres), gray mold (Botrytis cinerea), baby bean mildew (Erysiphe polygoni), sunflower seedweed (Plasmopora) (phytophthora infestans), and wheat germ (Pucolnia graminis f. sp. tritici species 158-2). It is preferred that the formulations have an active ingredient concentration of <2000 ppm.

In order to evaluate the antifungal efficacy of the active ingredient, a preliminary experiment was carried out by spraying the plants with the active ingredient at a concentration of 300 ppm and applying the carrier at 1690 liters / ha. 60

In general, potted plants are sprayed on a conveyor belt at the stage of their growth when they are susceptible to the fungal diseases to be evaluated and left to allow the spray to dry. The target plants were then infected with the spores of the 65 fungi, incubated until the disease developed, and the percentage reduction of the disease was read or estimated.

The following experimental methods were used to evaluate the antifungal activity of the formulations of the invention containing the compounds, enantiomorphs, salts or complexes as active ingredient.

Example A

Investigation of the effect of fungus (Helminthosporium teres) on barley-net mottling

Barley seedlings (Wong variant) were cut to 6.3 cm 24 hours prior to chemical treatment. With this operation, plants of the same height were created and thus the infected plants were rapidly infected and inoculated. The inoculation was done by spraying the chemical on the leaves of the plants with the help of a hand-atomizer until small droplets of the inoculum were visible on the leaves. The inoculated, inoculated plants were incubated for 24 hours in a humidified environment at 24-27 ° C before being placed in a greenhouse at 21-24 ° C. comparative studies 6-7 days after inoculation

We were done after 184,522 dos. Typical symptoms caused by Helminthosporium teres are initially irregular wet depressions which disappear and disappear as the lesion progresses. Many of the formulations of the present invention, when used against Helminthosporium teres, achieve complete inhibition when the active ingredient is present at a concentration of 300 ppm.

Example B.

Examination of the effect of gray mold (Botrytis fabae) on porcine leaves

Pig bean seedlings (Vida fabo variant) were cut to 11.5 cm 24 hours prior to chemical treatment. With this operation, plants of the same height were created and the treated plants were inoculated rapidly and to the same extent. Leaves of plants were sprayed on conveyor belts during inoculation of pig bean plants. The inoculated plants were incubated in a humid environment at 24-27 ° C for 66 hours. comparative studies were performed 66-68 hours after inoculation. Typical symptoms of porcine gray mold on leaf patches are regular round, spear or transient lesions on the leaves and trunk of the plant. Many formulations of the invention containing the active ingredient at a concentration of 300 ppm achieve greater than 70% inhibition against Botrytis dnerea.

Example C

Investigation of bean powdery mildew (Erysiphe polygoni)

Bean plants (Drawf Hort variant) were selected 24 hours prior to chemical treatment with two plant seedlings in each pot. The inoculum of the bean plants was sprayed with the inoculum spraying the leaves and stems until a uniform film of the inoculum was formed on the plant. The inoculated plants were kept under glasshouse conditions and comparative studies were performed 8-10 days after inoculation. Characteristic symptoms of bean powdery mildew are circular mycelial colonies on the leaf surface (fertilization). When used in many compositions of the invention against Erysiphe polygoni, complete inhibition can be achieved at a concentration of active ingredient of 300 ppm.

Example D

Investigation of the effect on polyhed grape mold (Plasmopora viticola)

Plasmopora viticola cultivars were grown on leaves of 10-12.5 cm tall grape seedlings (Siebel 1000 variants) and kept for 7 days at 18.5-24 ° C. The inoculum was then applied to the leaves of the plant with a hand-held spray gun and spraying continued until leaves of the same size were observed on the leaves. The inoculated plants were kept for the first 48 hours in a humid environment at 18.5-21 ° C and then placed in an incubator room. Characteristic symptoms of fluffy grape mold are pale yellow patches on the upper surface of the plant, varying in size and shape but most often circular with no sharp border. In humid environments, the lower leaf surfaces are covered by prominent fungal colonies. Many of the formulations of the present invention, when used against Plasmopora viticola, achieve greater than 90% inhibition when the active ingredient is present at a concentration of 300 ppm,

Example E

Investigation of the effect against the corncrake (Piricularia oryzae)

Rice seedlings (Nova 66 variant) were cut to 12.5 cm 24 hours prior to chemical treatment. With this operation, we created plants of the same height, thus allowing rapid inoculation and inoculation of the plants. The rice seedlings were inoculated by applying a spray gun to the leaves and stems of the plant and spraying until a uniform film of inoculum was formed on the leaves. The inoculated plants were incubated for 24 hours in a humid environment at 24-295 ° C before being placed in a greenhouse. comparative studies were performed 7-8 days after inoculation. They appeared as an initial rice patch. Typical lesions are large, gummy, gray-centered, brown-edged, 102 cm long, elliptical shapes. Many of the compositions of the invention can be used to achieve complete inhibition against Piricularia oryzae when the active ingredient is present at a concentration of 300 ppm.

Example F.

Investigation of the effect against Phytophthora infestans

6.2-7.5 cm tall tomato seedlings (Rutgers variant) were treated with water-soluble fertilizer 4-5 days prior to chemical treatment to promote rapid, succulent plant growth and improved symptoms. The spore suspension was applied to the leaves of the plant by means of a DeVübiss nebulizer at a pressure of 0.54-0.7 atm and spraying continued until droplets of the preparation were observed on the leaves of the plant. The inoculated plants were then kept for 4045 minutes in a humidified environment at 16-17 ° C and placed in a greenhouse at 21-24 ° C for 5 to 6 days after inoculation. Initial lesions of the tomato angle appeared as irregular, greenish-black, damp patches, which grew to become brown and wavy. Some lesions resembled frost damage. When used with many of the compositions of the invention against Phytophthora infestans, complete inhibition can be achieved when the active compound is concentrated at 300 ppm.

Example G

Study of the effect against wheat stalk (Puccinia graminis fsp.triciti species 15B-2) on day wheat plants (Monon variant) 24 hrs.

-101

Prior to chemical treatment 184,522 were cut to a height of 6.3 cm to ensure equal inoculation of the plants. Wheat stalk cultures on wheat seedlings were kept in a greenhouse for 14 days, and the above 6.3 cm wheat plants were inoculated with a suspension of the spores obtained from the culture. After inoculation with a 3.5 atm DeVilbiss nebulizer, the plants were placed in a humid chamber at 20 ° C for 12 hours in the dark using a self-timer and 3-4 hours in the light (5350 lux). The temperature in the chamber is max. 29 ° C. The plants were then allowed to dry slowly in an air stream and kept in a greenhouse for 2 weeks. The wheat angle appears on the stems and leaves of wheat seedlings as an irregularly shaped patch with brick red spores. Many formulations containing 300 ppm of active ingredient can achieve complete inhibition of wheat angle.

The efficacy data for the formulations used in the above assays are shown in Table ΙΠ. are summarized in Table.

Numbers and letters in the table mean:

Degree of phytotoxicity = slight damage = moderate damage = severe damage

Inhibition of disease:

A = 97-100% inhibition of disease

B = 90-96% inhibition of disease

C = 70-89% inhibition of disease

D = 50-69% inhibition of disease

E = <50% inhibition of disease - = not tested.

III. spreadsheet The example BH STICK BPM GDM RB TLB number 4-n-butyl E E E E E Night 1,2,4-triazole 1 THE E THE B E E 2 THE B THE B E 3 3 THE E THE C THE E 4 E C THE C THE E 5 THE E THE E C E 6 E E B E - THE 7 E E THE E - THE 10 E E THE E E E 11 E E THE E - THE 12 THE C THE C THE E 13 E E THE 3 THE 3 14 E E THE B B E 15 THE E THE C THE E 16 THE E THE bi E E 17 THE E THE B THE E 18 THE E THE C THE E 19 THE E THE E THE E 20 THE C THE E THE E 21 THE C THE C B E 22 E C THE E B E 23 E C Ei E THE THE 24 E E THE C THE E 25 B E THE C E B 26 THE C E E E E

The formulations of the present invention, formulated in various ways, may be applied to the seeds, soil or leaves of the plant. Formulations include, for example, wettable powders, emulsifiable concentrates, powders, granules, aerosols, or liquid emulsion concentrates, which contain the active ingredient in a liquid or solid carrier and, if necessary, a surfactant. These formulations contain from 0.00001% to 95% by weight of the triazole derivatives used as active ingredients.

It is usually desirable that the composition, especially when applied in the form of a spray on the leaves of the plant, contain various excipients, such as wetting agents, dispersing agents, binders, spray adjuvants, dispersants and the like.

In preparing solutions, the active compounds are usually dissolved in a solvent such as acetone, methanol, ethyl alcohol, dimethylformamide, pyridine or dimethylsulfoxide and diluted with water. The concentration of the solutions is 1 to 90%, preferably 5 to 50%.

Emulsifiable concentrates are prepared by dissolving the active ingredient together with an emulsifier in a suitable organic solvent or solvent mixture. The emulsifier allows the fungicide to form an emulsion with water. The concentration of active ingredient in the emulsifiable concentrate is usually from 10 to 90% by weight, and in the liquid emulsion concentrate is about 75% by weight.

In preparing wettable powders for nebulization, the active ingredient is admixed with finely divided solids, such as clay, inorganic silicates or carbonates, and silica, in addition to a wetting agent, spray adhesive, and / or dispersant. The concentration of the active ingredient in this formulation is usually 20-95% by weight. preferably 40-75% by weight

In the preparation of powder formulations, the active ingredient is mixed with finely divided solids such as silica, vegetable flour, silicate, carbonate or clay. The powder composition may also be prepared from a wettable powder by dilution with a finely divided carrier. Generally, a powder containing 20-80% by weight of the active ingredient is prepared and diluted in use so that the active ingredient content is 1-10% by weight.

The compositions of the invention, for example by means of a hydraulic nebulizer, a spray gun or an air pressure nebulizer, are generally used as a spray or powder. The amount of active ingredient used depends on a number of factors: it is usually advantageous to apply a composition per hectare in an amount of from 0.11 to 56 kg of active ingredient.

When applied to the seeds as a surface coat, the active ingredient is usually in the range of 7.7 g to 620 g per 100 kg of seeds.

When used as a soil contaminant, a formulation containing from 0.11 to 56 kg of active ingredient per hectare is applied either by soil application or surface treatment,

In the case of foliage treatment, usually 0.27 to 11.2 kg of active ingredient per hectare are used.

The compositions of the invention may also be used in combination with the following fungicides:

(a) dithiocarbamate and its derivatives, such as: iron (III) 11

-111

184,522 dimethyldithiocarbamate (ferban), zinc dimethyldithiocarbamate (current), magnesium ethylene bis-dithiocarbamate (maneb) and its coordination product with zinc (mancozeb) zinc-ethylene bis-dithiocarbamate (zineb), zinc propylene bis dithiocarbamate (propineb), sodium methyl dithiocarbamate (metham), tetramethylthiuram disulfide (thiram), zineb and polyethylene thiuram disulfide,

3,5-dimethyl-1,3,5-2H-tetrahydro-thiadiazine-2-thione (dazomet) and mixtures thereof with one another and / or with copper salts;

b) nitrophenol derivatives such as dinitro (1-methylphenyl) phenyl crotonate (dinocap).

2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate (binapacryl) and

2-sec-butyl-3,6-dinitrophenyl isopropyl carbonate;

c) heterocyclic compounds such as: N-trichloromethylthiothetrahydrophthalimide (captan), N-trichloromethylthiophthalimide (folpet), 2-heptadecyl-2-imidazole acetate (glyodine) 2-octylisothiazole-3 -you,

2,4-dichloro-6- (o-chloroanilino) -s-triazine, diethyl phthalimido phosphorothionate,

4-butyl-1,2,4-triazole,

5-amino-1- [bis (bimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,

5-ethoxy-3-trichloromethyl-1,2,4-triazole,

2.3-diciano-1,4-dithiananthraquinone (dithianon),

2-thio-1,3-dithio- [4,5-b] quinoxaline (thioquinox). methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate (benomyl),

2- (4 ', - Thiazolyl) -benzimidazole (thiabendazole),

4- (2-chlorophenylhydrazone) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide,

8-hydroxyquinoline sulfate and its metal salts,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxatin-4,4-dioxide,

2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxatin, α- (phenyl) -α- (2,4-cyclohexylphenyl) -5-pyrimidinyl methanol (triarimol), cis -N - [(1,2,3,2-tetrachloroethyl) thio] 4-cyclohexene-1,2-dicarboximide,

3- [2- (3,5-Dimethyl-2-oxycyclohexyl-2-hydroxy] -glutarimide (cycloheximide) but hydroacetic acid,

N- (1,2,2-tetrachloroethylthio) -3a, 4,7,7a-tetrahydrophthalimide (captafol),

5-Butyl-2-ethylamino-4-hydroxy-6-methylpyrimidine (ethyrimol)

4-Cyclododecyl-2,6-dimethylmorpholine acetate (dodemorph) and

6-methyl-2-oxo-1,3-dithiolo [4,5-b] quinoxaline (quinomethionate);

(d) various halogenated fungicides such as: tetrachloro-p-benzoquinone (chloranyl),

2.3-dichloro-1,4-naphthoquinone (dichlone),

1,4-dichloro-2,5-dimethoxybenzene (chloroneb),

3.5.6 - trichloro-o-anisic acid (tricamba),

2.4.5.6-tetrachloroisophthalonitrile (TCPN),

2.6-dichloro-4-nitroaniline (dichlorane),

2-chloro-1-nitropropane, polychlorinitrobenzenes such as pentachloronitrobenzene (PCNB) and tetrafluorodichloroacetone,

(c) fungicidal antibiotics such as:

griseofulvin, kasugamycin and streptomycin,

(f) copper-containing fungicides such as: copper (I) oxide, basic copper (II) chloride, basic copper carbonate, copper naphthanate and Bordeaux mixture; and

(g) various fungicides such as:

diphenyl, dodecylguanidine acetate (dodine), phenylmercury acetate, N- (ethylmercury) -1,2,3,6-tetrahydro-3,6-endomethane-3,4,5,6,7 , 7-hexachlorophthalimide, phenylmercury monoethanolammonium lactate, p-dimethylaminobenzene diazonium sulfonate, methyl isothiocyanate, 1-thiocyano-2,4-dinitro benzene, 1-phenylthiosemicarbazide, nickel-containing compounds, calcium cyanamide, lime sulfur, sulfur, and 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene-thiophenat-methyl.

The compositions of the present invention have broad spectrum fungicidal activity and are thus well suited for storage of grain. Metal salt complex formulations can be used as fungicides for lawns, orchards, vegetable gardens and golf courses. Other applications of the compositions of the invention containing 1- and 4-substituted-1,2,4-triazoles are also possible for agricultural and horticultural professionals.

The composition of some of the compositions of the invention is described below:

(1) Wettable powder part by weight of 1- [beta (2,4-dichlorophenyl) hexyl] -1,2,4-triazole, part by weight of silica (Hi-Sil (K)) part by weight of sodium lignin sulphonate (a) instead of silica we can use Barden clay).

(2) Por

0.001 parts by weight of 1- [beta, beta-tetramethylene-beta- (2,4-dichlorophenyl) ethyl] -1,2,4-triazolyl chloride

99.999 parts by weight of silica (3) Emulsifiable concentrate by weight of 1- [beta (2,4-dichlorophenyl) hexyl] -1,2,4-triazolium nitrate, part by weight of water, part by weight of alkylated phthalic acid glycerol ( TritonW B-1956 (R) (4) Concentrate% by weight of 1- [2-cyano-2- (2,4-dichlorophenyl) hexyl] -1,2,4-triazolium nitrate% by weight of silica ( 5) Solution for spraying

0.00001% by weight of 1- [2-dano-2-phenylhexyl] -1,2,4-triazole

99.99999% by weight of solvent containing 25% by weight of acetone,% by weight of methanol and 50% by weight of water.

Claims (2)

Patent claims CLAIMS 1. A fungicidal composition comprising as active ingredient from 0.00001 to 95% by weight of a triazole derivative, optionally in the form of an agriculturally acceptable enantiomorph, or in the form of an acid addition salt or a metal complex thereof, -121 184 522 - Z is phenyl optionally substituted with one or two halogen atoms or C 14 alkyl or phenoxy, R ¹ is cyano or C 1-12 alkyl, 5 - R ² is hydrogen, C 1 -C 8 alkyl or allyl; or - R ¹ or R ² together with the carbon atom to which they are attached are Cyclopentyl; and - Q is 1- (1,2,4-triazolyl) - or 4- (1,2,4-10) triazolyl), in the presence of a liquid or solid carrier or diluent, preferably silica, acetone, methanol, water and optionally a surfactant, preferably sodium lignin sulfonate. ¹ 5 A process for the preparation of triazole derivatives wherein, in the general formula (IX): - Z is phenyl optionally substituted with one or two halogen, or C 14 alkyl or phenoxy groups; - R ¹ is cyano or C 1-2 alkyl; - R ² is hydrogen, C 1-8 alkyl or allyl; or - R ^{1 and} R ² together with the carbon atom to which they are attached form a cyclopentyl group, wherein the compound of formula (V) - Z, R ¹ and R ² are as defined above - (VI), in an inert solvent; at reflux temperature in the presence of an organic sulfonic acid catalyst, preferably p-toluenesulfonic acid, benzenesulfonic acid or methanesulfonic acid.