CS199723B2 - Fungicide and process for preparing effective compounds - Google Patents

Abstract

Imidazole derivatives have the following formula <IMAGE> in which X is identical or different and denotes halogen, lower alkyl, nitro or lower haloalkyl, n is 1 or 2 and Y denotes alkoxy lower alkyl, lower alkenyloxyalkyl, lower phenoxyalkyl, substituted lower phenoxyalkyl or benzyl, with the proviso that Xn denotes trifluoromethyl in the 2 position and chlorine in the 4 position when Y represents benzyl. The compounds may be present as complexes of metal salts. A fungicide contains as at least one active component a compound of the formula I. The compounds of the formula I are obtained by reacting imidazole with a halide which donates the radical <IMAGE>

Description

FIELD OF THE INVENTION The present invention relates to fungicidal compositions containing novel imidazole derivatives and metal complexes thereof, to a process for the manufacture of said active compounds and to a method for combating fungi.

Japanese Patent Application Publication No. 39674/77 discloses that certain imidazole derivatives exhibit fungieid activity. These imidazole derivatives correspond to the general formula

in which

R ‘represents an alkyl group,

Z ‘represents a halogen atom, a nitro group, a lower alkyl group or a lower alkoxy group and n is a number> 0, 1 or 2.

Japanese Patent Application Publication No. 46071/77 also discloses that some other imidazole derivatives exhibit fungieid activity. These imidazole derivatives correspond to the general formula r \

n ^ n ~ c = n

II n in which

X 'represents a methyl group, a chlorine atom, a bromine atom, a nitro group or a trifluoromethyl group and n is an o number. 1 or 2.

Although these known imidazole derivatives are fungicidal. their activity is not sufficient and these compounds are phytotoxic to plants. The known compounds mentioned above cannot therefore be used in practice as fungicides.

It has now been found that the imidazole derivatives of the general formula I

(I) where

Y is R1-O-R2 or benzyl, n 'is 1 or 2,

X represents a chlorine atom, a bromine atom, an alkyl group having 1 or 2 carbon atoms, a nitro group or a trifluoromethyl group, where, when n is 2, the individual substituents of X may be the same or different,

R 1 is C 1 -C 4 alkylene;

R @ 2 represents a C1 -C8 alkyl group, an allyl group, a phenyl group or a methyl group substituted by a methyl group and / or chlorine, and the metal complexes of these imidazole derivatives exhibit excellent fungicidal activity and are not phytotoxic to plants.

Preferred fungicides are compounds of the formula

and metal complexes thereof, and compounds of formula (Ia)

/ = \

in which

X1 is chlorine or trifluoromethyl,

R 1 represents an alkylene group having 1 or 2 carbon atoms, such as methylene, methylmethylene or ethylene;

R2 represents a C2-C4 alkyl group or an allyl group, and their metal complexes.

The active compounds according to the invention can be prepared according to the following reaction scheme

/ ~ - »

IN ^ NIH

in which

Hal represents a halogen atom and

Y, X and n are as defined above.

The reaction is carried out in an inert solvent in the presence of a basic condensing agent such as sodium carbonate. potassium carbonate, sodium hydroxide, sodium methoxide, trimethylamine, triethylamine, pyridine or piperidine. As an inert solvent, chloroform, dichloromethane, benzene, toluene, xylene, chlorobenzene, acetonitrile, acetone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide or dioxane can be used. It is generally carried out at a temperature of from 0 ° C to the boiling point of the reaction solution, preferably at a temperature of 40 ° C to the boiling point. The reaction is usually complete in 1 to 3 hours. After completion of the reaction, the reaction solution was washed with water and dried. If necessary, washing and drying can be carried out only after replacement of the original solvent with another. The solvent is then distilled off to give the title compound. The metal complexes of the invention can be prepared according to the following reaction scheme:

in which

AB is an organic or inorganic metal salt,

A represents a divalent or trivalent metal atom,

B · represents the anionic component of the salt and

I represents the number of valences of the metal atom A in the metal salt AB, and the remaining general symbols have the meaning given above.

As the metal salt, chloride, sulfate, nitrate or acetate of copper, zinc, nickel, cobalt, manganese, iron or silver can be used. Copper sulphate, copper chloride, zinc chloride or acetate are preferably used. zinc. In the practice of the metal complex reaction, the imidazole derivative is dissolved in an inert solvent, the metal salt is added to the solution, and the mixture is allowed to react with stirring. The reaction is generally carried out at room temperature for several minutes. Any inert solvent miscible with the water-miscible imidazole derivative may be used as the inert solvent. Usually ethyl acetate, methanol, acetone / tril, dioxane are used. or · tetrahydrofuran. After completion of the reaction, the reaction mixture is poured into n-hexane or water and the precipitated crystals are filtered off to give the metal complex of the invention.

The preparation of the compounds of the invention is illustrated by the following non-limiting examples.

Example 1

1- [N- (2-Bromophenyl) -2-ethoxypropane] imidoyljimidazole · (Compound No. 3) '

II g of 2 * -bromo-2- (ethoxy) propionanilide was reacted under reflux for 30 minutes with 8.4 g of phosphorus pentachloride in 50 ml of chloroform. The by-product chloroform and phosphorus oxychloride are distilled off and the residue is dissolved in 40 ml of acetonitrile. 2.8 g of imidazole and 4.1 g of triethylamine are added to the solution and the mixture is refluxed for 3 hours. After completion of the reaction, the acetonitrile is distilled off, the residue is washed several times with water and dried over anhydrous magnesium sulfate. After distillation of the dichloromethane, the residual oily product was purified by silica gel chromatography using dichloromethane as eluent. 4 g of the desired compound are obtained having a refractive index n _D -5 = 1.5870.

Example 1 a d 2

1- [N- (2,4-Dichlorophenyl) -2-propoxypropanimidoyljimidazole (Compound No. 9)

7.5 g of 2 ', 4'-dichloro-2- (propoxy) propioinanide are reacted for 30 minutes with 5.6 g of phosphorus pentachloride in 40 ml of chloroform at reflux temperature of the reaction solution chloroform and phosphorus oxychloride The by-product formed is distilled off under reduced pressure and the residue is dissolved in 40 ml of acetonitrile. 1.9 g of imidazole and 2.7 g of triethylamine are added and the mixture is refluxed for 3 hours. After completion of the reaction, 4 g of the title compound of melting point 68 DEG-69.5 DEG C. are obtained by analogous work-up as in Example 1.

Example 3

1- [N- (4-Sulfon-2-yl-fluoromethylphenyl) -2-allyloxypropanimidoyl] imidazole (Compound No. 11)

9.3 g of 4'-chloro-3'-trichloro-2 - ((allyoxy) propionanilide is reacted with 6.3 g of phosphorus pentachloride in 40 ml of chloroform for 30 minutes while heating the reaction solution to reflux. The chloroform and phosphorus oxychloride are distilled off, the residue is dissolved in 40 ml of acetonitrile, 2.1 g of imidazole and 3 g of t-amine are added and the mixture is refluxed for 3 hours. The reaction mixture was worked up as in Example 1 to give 5 g of the desired compound having a refractive index nD- = 1.5440.

Example 4

1- [N- (2,4-Dichlorophenyl) -2-butoxypropanimidohl] imidazole (Compound No. 19)

8.8 g of 2‘, 4‘-dichloro-2- (butoxy) propionanilide are treated with 6.4 g of phosphorus pentachloride in 40 ml of chloroform for 30 minutes while refluxing the reaction solution. The chloroform and phosphorus oxychloride were distilled off, the residue was dissolved in 40 ml of acetonitrile, 2.1 g of imidazole and 3 g of triethylamine were added to the solution, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the reaction mixture was worked up as in Example 1 to obtain

4.5 g of the desired compound having a refractive index n _D 25 · ⁵ = 1.5682.

Example 5

1- [N- (2,4-Dichlorophenyl) -3-propoxypropanimidoyl] imidazole (Compound No. 36)

6.9 g of 2 ‘, 4‘-dichloro-3- (propoxy) propionanilide and 8 g of triethylamine are dissolved in 30 ml of chloroform and introduced into the solution under ice-cooling at 0 to 10 T.

3.7 g of phosgene · After warming the solution to room temperature, the resulting solution is stirred for 2 hours and then 2 g of imidazole are added. The mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with water, and dried over anhydrous magnesium sulfate. After distilling off the chloroform from the solution, 7.7 g of the desired compound are obtained with a refractive index ni29 = 1.5688.

Example 6

1- [N- (4-Chloro-2-trifluoromethylphenyl) -2-propoxyacetimidoyl] imidazole (Compound No. 37)

12.6 g of 4‘-chloro-2‘-trifluoromethyl-2- [propoxy] acetanilide and 12.9 g of triethylamine are dissolved in 80 ml of chloroform and a solution of 6.4 g of phosgene in 30 ml of chloroform is added dropwise. · Resulting. the solution is stirred at room temperature for 1 hour, then 4.4 g of imidazole and. the mixture was stirred at room temperature for 15 hours. After completion of the reaction, the chloroform was distilled off, the residue was dissolved in n-hexane, the solution was washed with water and dried over anhydrous magnesium sulfate. Distilling off the n-hexane and purifying the residue by chromatography on silica gel affords 9.8 g of the desired compound, m.p. 66-66.5 ° C.

Example 1 a d 7

1- [N- (trifluoromethylphenyl) -sek.butoxyacetim.idoyl] imidazole (compound no. 39) g of 4 ^{<-chloro-2htfifluormethyl} seb.butoxyacetanilidu was allowed to react for 1 hour with 5.2 g of phosphorus pentachloride in 50 ml of benzene at reflux the reaction solution. Benzene and phosphorus oxychloride are distilled off under reduced pressure, the residual oily substance is dissolved in 50 ml of chloroform, 1.7 g of imidazole and triethylamine are added to the solution, and the resulting mixture is heated at 50 DEG for 1 hour with stirring. C.

After completion of the reaction, the reaction solution is washed with water and dried, and the chloroform is distilled off. Purification of the residue by silica gel chromatography affords 1.85 g of the desired compound with a refractive index 21 21 = 1.5378.

Example 8

1- [N- [4-Chloro-2-trifluoromethylphenyl) -2-ethoxyacetimidoyl] imidazole (Compound No. 40) g 4'-Chloro-2'-trifluoromethyl-2- (ethoxy) acetanilide and 10,8 g of triethylamine is dissolved in 80 ml of chloroform, and a solution of 5.3 g of phosgene in 30 ml of chloroform is added dropwise.

The resulting solution was stirred at room temperature for 1 hour, then 2.9 g of imidazole was added thereto, and the mixture was stirred at room temperature for 15 hours. After completion of the reaction, the chloroform is distilled off, the residue is dissolved in n-hexane, the solution is washed with water and dried over anhydrous magnesium sulphate. After distilling off the n-hexane from the solution, 10.2 g of the desired compound are obtained, m.p. 49-52 ° C.

Example 9

1- [N- (2,4-Dichlorophenyl) -4-chloro-2-methylphenoxyacetimidoyl] imidazole (Compound No. 43)

3.4 g of 2, 4 &apos; -dichloro- [4-chloro-2-methylphenoxy] acetanilide were treated with 2.3 g of phosphorus pentachloride in 40 ml of benzene for 1 hour while refluxing the reaction solution. The benzene and phosphorus oxychloride are distilled off under reduced pressure, the oily residue is dissolved in 40 ml of chloroform, 0.75 g of imidazole and 1.1 g of methylamine are added to the solution, and the mixture is stirred at 50 DEG C. for 1 hour. Deň: 32 ° C. After completion of the reaction, the reaction mixture was worked up analogously to Example 7 to give 1.1 g of the desired compound as a crystal melting at 84-86 ° C.

Example 10

1- [N- (4-Chloro-2-trifluoromethyl-phenyl) -3-ethoxy-amino-yoyl] -imidazole (Compound No. 46)

6.5 g of 4‘-chloo-2‘-trifluoromethyl-2- (ethoxy) -topionanilide were treated with 4.9 g of phosphorus pentachloride in 30 ml of chloroform under reflux for 1 hour. The chloroform and phosphorus oxychloride are distilled off under reduced pressure, 3.2 g of imidazole and 30 ml of acetonitrile are added to the residue, and the mixture is refluxed for 30 minutes. After completion of the reaction, the acetonitrile is distilled off, the residue is dissolved in dichloromethane, the solution is washed with water and dried over anhydrous magnesium sulphate. After distilling off the solvent from the solution, the residue is purified by chromatography on an alumina column to give 3.5 g of the desired compound, m.p. 61-62 ° C.

Example 11 1- [N- (4-Chloro-2-trifluoromethyl-phenyl) -phenylacetimidoyl] -imidazole [Compound No. 56]

3.5 g of N- (4-chloro-2-trifluoromethylphenyl) phenylacetamide were reacted with 2.6 g of phosphorus pentachloride in 40 ml of benzene under reflux. After completion of the reaction, the benzene and phosphorus oxychloride are evaporated, the remaining N- [4-chloro-2-trifluoromethylphenyl) phenylacetimidoyl chloride is dissolved in 50 ml of acetonitrile and 0.85 g of imidazole is added with stirring.

1.3 g of triethylamine are successively added to the resulting solution while cooling, the mixture is heated at 60 ^DEG C. for 30 minutes, then the acetonitrile is distilled off, the residue is dissolved in 60 ml of dichloromethane, the solution is washed with water and dried. The dichloromethane was distilled off and the oily residue was purified by silica gel column chromatography. 2.1 g of the expected compound are obtained, m.p. 79-81 ° C.

Example 12

Bis [1- (N- (2,4-dichlorophenyl) -2-propoxypropanimidoyl) imidazole] copper (II) chloride [Compound No. 57] g 1- [N- (2,4-dichlorophenyl) -2-propoxy propanimidoyl] imidazole is dissolved in 5 ml of methanol and 0.5 g of anhydrous copper chloride is added to the solution. The mixture was stirred at room temperature for 5 minutes, then poured into water (100 mL) to precipitate crystals. The crystals were filtered off, washed with water and n-hexane and then dried under reduced pressure. 1 g of the desired complex is obtained, m.p. 165-169 ° C.

Example 13

Zinc chloride [1- (N- (2,4-dichlorophenyl) -2-propoxypropanimidoyl) imidazole] chloride (Compound No 58)

Treatment of 2 g of 1- [N- (2,4-dichlorophenyl) -2-proipoxypropammidoyl] imidazole with 0.5 g of anhydrous zinc chloride, carried out in an analogous manner to that of Example 12, affords 2 g of the desired complex, m.p. 157-158. Deň: 32 ° C.

Example 14

Bis [1- (N- (4-chloro-2-trifluoromethylphenyl) phenylacetimidoyl) imidazole] copper (II) chloride (Compound No. 82) g 1- [N- (4-chloro-2-trifluoromethylphenyl) phenylacetimidoyl] imidazole was reacted with 0.5 g of anhydrous cuprous chloride in a manner analogous to that of Example 12 except that ethyl acetate was used as the reaction medium instead of methanol. 2 g of the desired complex are obtained, m.p. 105-108 ° C.

Examples of active ingredients produced by the process of the invention. are summarized in Tables 1 and 2 below:

Table 1

Compound number X „Y Physical constants (melting point in ° C)

1 2-F —CH — O — C2H5 n _D ^23-5 1.5585 1 СНз 2 2-Br -СЧ-О- ^ У n _D 26 1.6222 3 2-Br —CH — O — C2H5 n _D 25 1.5870 4 2,4-012 1 СНз —CH — О — СНз n _D 2i 1.5800 5 2,4-Ch С3Н7-П —CH — O — C2H5 n _D ²⁴ 1.5833

СНз

Compound number χ " Y Physical constants (melting point in ®C) 6 2-CF3-4-C1 —CH — 0 — СНз 1 n _D ²¹ 1.5430 7 2-CF3-4-C1 1 СЗН7-П —CH — O — C2 H5 n _D 2i 1.5340 8 2,4-Brz СНз —CH — O — C2 H5 n _D ²⁵ 1.6090 9 2,4-012 CH3 —CH — 0 — С3Н7-П (68 to 69.5) 10 2,4-012 СНз —CH — O — CH2CH - CH2 1 n _D 25 1.5705 11 2-CF3-4-C1 СНз —CH — O — CH2CH = CH2 n _D ²² 1.5440 12 2-СНз СНз —CH — O — C2 H5 1 n _D ²² 1.5620 13 2-NO2 СНз —CH — O — C2H5 [ 73 - 76 14 2-CF 3 СНз —CH — O — C2 H5 n _D ²³ · ⁵ 1.5292 15 Dec 2-ΒΓ-4-ΝΟ2 СНз —CH — O — C2 H5 (160-161) 16 2-C1 1 СНз —CH — O — C2 H5 n _D ²⁵ · ⁵ 1.5720 17 2-CF3-4-C1 СНз —CH — 0 — С3Н7-П n _D ²⁵ · ⁵ 1.5300 18 2-Br 1 СНз —CH — 0 — С3Н7-П n _D ²⁵ · ⁵ 1.5820 19 Dec 2,4-012 СНз —CH — 0 — С4Н9-П n _D ²³ · ⁵ 1.5682 20 May 2-CF3-4-C1 СНз —CH— '0— С4Н9-П 1 n _D ²⁵ - ⁵ 1.5295 21 2-C 1-5 -CH 3 1 СНз —CH — O — C2 H5 n _D ²⁵ 1.5668 22nd 2,4-C12 1 СНз —CH — O — C3H7-1 n _D ²⁷ · ⁵ 1.5700 23 2-CF3-4-C1 1 СНз —CH — O — C3H7-1 86 - 87 24 2.4-C12 1 СНз —CH — O — C4H9-1 n _D ²⁷ · ⁵ 1.5684 25 2-CF3-4-C1 СНз —CH — O — C4H9-1 I n _D ²⁷ · ⁵ 1.5275 26 3,4-Clz 1 СНз —CH — O — C2 H5 n _D ² »1.5782

СНз

Compound number

Χη

Physical constants (temperature: melting in ° C)

2-С2Н5 —СН — О-С2Н5 2-NO2-4-C1 СНз —СН — 0 — С2Н5 2-NO 2-6 -CH 3 | СНз —СН — 0 — С2Н5 AND 4-С1 1 СНз —СН — 0 — С4Н9-11 2-С1 СНз —СН — 0 — СзН7-п 2,4-012 СНз 2-CF3-4-C1 -о 2-CF3-4-C1 -СН-О-СНС2Н4 2,4-012 СНз СНз —СН — 0 — СНС2Н5 2,4-012 СНз СНз - (СН2) 2—0 — СзН7-П 2-CF3-4-C1 —СН2—0 — С3Н7-П 2,4-012 —СН2—0 — С5Н7-П 2-CF3-4-C1 —СН2—0 — СН2Н5 2-CF3-4-C1 | СНз —СНг — 0 — С2Н5 2,4-012 —CHž — 0 — С2Н5 2-CF3-4-C1 сн ₃ 2,4-012 2,4-012 - (СН2) 2—0 — С2Н5 2-CF3-4-C1 - (СН2) 2—0 — СзН7-П 2-CF3-4-C1 - (СН2) 2—0 — С2Н5 2-CF3-4-C1 —СНг— 0 — С4Н9-П 2-CF3-4-C1 —СНг — 0 — СН — С3Н7-П 2,4-012 СНз —СНг — 0 — СН — С3Н7-П 2,4-012 | СНз —СНг — 0 — С4Н9-П 2-CF3-4-C1 —СНг — 0 — С5Н11-П 2,4-012 —СНг — 0 — СэНи-п 2-CF3-4-C1 —СНг — 0 — C3H7-I 2,4-012 —СНг — 0 — C3H7-I 2-CF3-4-C1 —СНг — 0 — CeH17-n 2-CF3-4-C1

n _D ²⁷ 1.5541 n _D ²⁷ 1.5959 n _D ²⁷ 1.5799 n _D ² 1,5 1.5690 n _D ³¹ · ⁵ 1.5650 n _D ² 4 1.6171 (90-93) n _D ²⁰ 1, 5382

По ² ® 1.5692

По ²⁹ 1.5688 (66 - 66.5) no ²⁷ 1.5765 n _D 34 1.5292 (49 - 52)

По ²⁷ 1.5962

По ²⁰ 1.5875 (84 - 86) n _D ²⁰ 1.5952

По ²⁷ 1.5463 (61 - 62)

По ²³ 1.5369 n _D ²² 1.5295

По ²² 1.5705

По ²² ' ⁵ 1.5765

По ²² · ⁵ 1.5300 n _D ²² · ⁵ 1.5717

По ²² · ⁵ 1.5363 (52-53)

По ²⁴ 1.5225 (79-81)

Table 2

AB Physical constants (melting point in ° C)

Slouče- X _n nlna number ·

Y

57 2,4-C12 58 2,4-012 59 2,4-012 60 2-CF3-4-C1 61 2-CF3-4-C1 62 2-CF3-4-C1 63 2-CF3-4-C1 64 2-CF3-4-C1 65 2-CF3-4-C1 66 2-CF3-4-C1 67 2-CF3-4-C1 68 2-CF3-4-C1 69 2-CF3-4-C1 70 2,4-012 71 2,4-012 72 2-CF3-4-C1 73 2,4-012 74 2-CF3-4-C1 75 2-CF3-4-C1 76 2-CF3-4-C1 77 2,4-012 78 2-CF3-4-C1 79 2,4-012 80 2,4-012 81 2,4-012

2-CF3-4-C1

—CH — О — С3Н7-П AND ; cuci2 (165—169) 1 СНз —CH — О — С3Н7-П ZnC12 (157—158) CHs —CH — О — С3Н7-П 'CUSO4 (90—94) СНз —CH — O — C3H7-11 ZnC12 (48—53) СНз —CH — O — C2H5 ZnC12 (71—75) СНз —CH2— О — C2H5 ZnC12 (52—56) —CH2-0 — C2H5 CUS04 (91-94) - (СНг) 2—0 — C2H5 CUSO4 (138—141) —CH2—0 — С4Н9-П ZnC12 (58—64) —CH2— — —S3Н7-П CUSO4 (77—81) —CH2— — —S3Н7-П ZnC12 (71-74) —CH — O — CHC2H5 CUSO4 (76—78) 1 1 СНз СНз —CH — O — CHC2H5 1 '1 ZnC12 (64—661 1 1 СНз СНз —CH2—0 — С4Н9-П CUSO4 (117—1201 —CH2—0 — С5Н11-П CuS04 (103—108) —CH2-0 — C3H7-I CUSO4 (81—86) —CH2-0 — C3H7-I CuSO4 (132—138) —CH2—0 — С5Н11-П CuSOi (144-151) —CH2—0 — С5Н11-П ZnC12 (55—64) —CH2-0 — C3H7-1 ZnC12 (83—88) —CH2—0 — CH — С3Н7-П CuS04 (78—80) 1 СНз —CH2—0 — CH — С3Н7-П CuS04 (74—76) 1 СНз —CH — 0 — С3Н7-П , iFeC13 (50-56) 1 СНз —CH — 0 — С3Н7-П Cu (CH3- (138—141) 1 C00) 2 СНз —CH — 0 — С3Н7-П Zn (CH3- (128—130) СНз C00) 2

CuClz (105—108)

Zn (CH3 - (42—46))

COO) 2

2-CF3-4-C1

*) the symbol 1 corresponds to the number of valences of the metal atom A in the metal salt AB

Of the compounds listed in Tables 1 and 2, Compounds No. 9, 11, 17, 22, 23, 34, 36, 37, 38, 39, 40 and 56, and metal complexes thereof, such as, are preferred as fungicides. compounds No. 57, 58, 59, 62, 63, 82 and 83.

Most metal complexes have better fungicidal activity and better residual activity than the corresponding free imidazole derivatives.

As already mentioned. above, it has been found that the compounds of the invention, when used to prevent plant damage, exhibit fungicidal activity.

These compounds can control a wide variety of fungal diseases of leaves, fruits, stems and roots of cultivated plants without damaging these plants.

Examples of numerous fungi against which the compounds are effective include, but are not limited to, the following fungal diseases: gray mold, sclerotia rot, seedlings and vegetable mildew, brown peach rot, corn leaf blotch, apple scab and pear, pear rust, powdery mildew of apple and rust on various crops.

Said compounds are particularly effective against powdery mildew, scab and rust.

Another advantage is that these compounds are not. for plants phytotoxic.

The invention also encompasses the use of liquid or solid compositions containing as active ingredient one or more of the aforementioned substances.

The compounds of the invention may be used directly, without mixing with a suitable carrier.

The active compounds according to the invention may be formulated by mixing with suitable carriers to form conventional pesticidal compositions such as wettable powders, emulsifiable concentrates, dusts, granules, water-soluble powders and aerosols. Hentonite, e.g. . i-nfusorium clay, apatite, gypsum, talc, pyrophyllite, vermiculite and clay. Liquid carriers include, for example, kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, benzene and water. If desired, it is possible to obtain a homogeneous and stable formulation add ^one surfactant.

In the case of using the metal complexes of the invention as active ingredient may be finished instead of the metal complex, ^one may also use a mixture of the corresponding free imidazole derivative and metal salt. In particular, the free imidazole derivative may be mixed with a metal salt such as zinc chloride, copper chloride or copper sulfate to prepare the fungicidal composition or to apply it to plants. In addition to the metal salts mentioned above, metal-containing pesticides such as mancozeb, oxine-copper or phencyl hydroxide can be mixed with the imidazole derivatives.

The concentration of active ingredient in the fungicidal composition according to the invention may vary depending on the type of composition and varies. for example in the case of wettable powders from 5 to 80% by weight, preferably from 20 to 80% by weight, in the case of emulsifiable concentrates from 5 to 70% by weight, preferably from 10 to 50% by weight, and in the case of dusts from 0.5 · to 20% by weight, preferably ¹ to 1 10% by weight.

A wettable powder or an emulsifiable concentrate containing a greater amount of the active ingredient can be suspended or emulsified in water and then applied by spraying onto the leaves of the plants or the site to be protected.

The compounds of the invention may also be used in admixture with other fungicides, insecticides, acaricides and herbicides.

The following are non-limiting examples of the fungicidal compositions of the present invention.

Example 15

Wettable powder

Ingredients:

Component Parts by weight Compound No. 9 40 diatomaceous earth 53 higher alkyl sulfate 4 alkylnaphthalenesulfonic acid acid 3 Preparation:

The above ingredients are homogeneously mixed and ground to a fine particle size to give a wettable powder containing 40% active ingredient. In use, this wettable powder is diluted with water to the desired concentration and sprayed as a suspension.

Example 16

Emulsifiable concentrate

Ingredients:

Component Parts mass compound No. 5630 xylene33 dimethylformamide 30.

pflyoxyethylene-alkylallyl ester7

Preparation:

The above ingredients are released with stirring to give an emulsifiable concentrate containing 30% of the active ingredient. When in use. The concentrate is diluted with water to the desired concentration and sprayed in the form of an emulsion.

Example 17 Dust Ingredients: Component Parts by weight Compound No. 62 10 talc 89 polyoxyeehylene-alkylallyl ether 1

Preparation:

The above ingredients are homogeneously mixed and ground to a fine particle to give a dust containing 10% active ingredient. In use, the composition is applied directly.

The fungicidal activity of the compounds of the invention is illustrated by the following tests:

Test 1

Effectiveness test on gray mold on bean

The cut bean leaves (Phaseolus vulgaris) are immersed for about 30 seconds in an aqueous suspension prepared by diluting a wettable powder to a test compound concentration of 200 ppm. After air drying, treated leaves are inoculated with Botrytis cinerea mycelium and kept in a humid chamber at 20 ° C. Efficacy is evaluated 4 days after inoculation. The results are summarized in Table 3 below.

Test 2

Test of effectiveness on powdery mildew on cucumbers

The leaves of the seedlings in the cultivated cucumber pot (var. Satsukimidori) at stage 1 to 2 ' After air-drying, treated leaves are inoculated with conidia of Sphaerotheca fuliginea and kept in a greenhouse at 25 ° C for 9 days, after which the effect is evaluated. The results are summarized in. the following tables 3.

Test 3

Efficiency test for rhizoctonium cucumber fall

Cucumber (var. Suyo) uterine plants are treated by injection of an aqueous suspension containing the test compound at a concentration of 100 ppm into the soil (10 ml / pot with 7 germinate plants), and inoculated with mycellia of the fungus Rhizoctonia solani (potato spice) . The effect is evaluated 4 days after inoculation. The results obtained are summarized in Table 3 below.

TABLE 3

Effect in%

Compound number test 1 test 2 test - 3

1 99 2 93 84 3 100 ALIGN! 97 100 ALIGN! 4 100 ALIGN! 100 ALIGN! 5 100 ALIGN! 100 ALIGN! 6 100 ALIGN! 100 ALIGN! 7 100 ALIGN! 100 ALIGN! . 100 ALIGN! 8 100 ALIGN! 100 -. 9 100 ALIGN! 100 ALIGN! 100 ALIGN! 10 100 ALIGN! . 95 11 100 ALIGN! 100 ALIGN! 100 ALIGN! 12 100 ALIGN! 95 13 100 ALIGN! 89 14 100 ALIGN! 100 ALIGN! 100 ALIGN! 15 Dec 100 ALIGN! 95 16 100 ALIGN! 95 100 ALIGN! 17 100 ALIGN! 100 ALIGN! 100 ALIGN! 18 100 ALIGN! 100 ALIGN! 100 ALIGN! 19 Dec 100 ALIGN! 95 100 ALIGN! 20 May 100 ALIGN! 100 ALIGN! 100 ALIGN! 21 100 ALIGN! 100 ALIGN! 86 22nd 100 ALIGN! 100 ALIGN! 100 ALIGN!

Compound number test 1 Effect in% test 2 test 3 23 100 ALIGN! 100 ALIGN! 100 ALIGN! 24 100 ALIGN! 100 ALIGN! 86 25 100 ALIGN! 100 ALIGN! 100 ALIGN! 26 100 ALIGN! 27 Mar: 100 ALIGN! 100 ALIGN! 95 28 100 ALIGN! 89 29 100 ALIGN! 100 ALIGN! 30 100 ALIGN! 87 36 95 37 93 100 ALIGN! 100 ALIGN! 38 95 100 ALIGN! 100 ALIGN! 39 100 ALIGN! 100 ALIGN! 100 ALIGN! 40 95 100 ALIGN! 100 ALIGN! 41 100 ALIGN! 79 42 90 86 43 95 100 ALIGN! 45 100 ALIGN! 100 ALIGN! 46 100 ALIGN! 100 ALIGN! 51 95 100 ALIGN! 95 52 95 95 95 55 95 100 ALIGN! 95 56 100 ALIGN! 100 ALIGN! 100 ALIGN! 57 100 ALIGN! 100 ALIGN! 100 ALIGN! 58 100 ALIGN! 100 ALIGN! 100 ALIGN! 59 100 ALIGN! 100 ALIGN! 100 ALIGN! 60 100 ALIGN! 100 ALIGN! 100 ALIGN! 61 100 ALIGN! 100 ALIGN! 100 ALIGN! 62 100 ALIGN! 100 ALIGN! 100 ALIGN! 63 100 ALIGN! 100 ALIGN! 100 ALIGN! 64 100 ALIGN! 100 ALIGN! 82 96 100 ALIGN! 83 100 ALIGN! comparative compounds *) 1 63 0 ** 2 90 3 90 4 90 not saved 0 0 0

*) Comparative compounds

(Japanese Published Patent Application No. 39674/77) = Euparene: N-dichlorofluoromethylthio-N, N-dimethyl-N'-phenylsulfonamide = Morestane: 6-methyl-1,3-dithiolo [4,5-b] quinoxaline- 2-on = PCNB: pentachloronitrobenzene

') Observed phytotoxicity

Claims (12)

I will invent the subject 1β What is claimed is: 1. A fungicidal composition comprising an inert carrier and a fungicidally effective amount of an imidazole derivative of the formula (I) as an active ingredient wherein: Y is R1-O-R2 or benzyl, n is 1 or 2, X is a chlorine atom, a bromine atom, an alkyl group having 1 or 2 carbon atoms, a nitro group or a trifluoromethyl group, and when n has the value 2 the individual substituents in the meaning of X may be the same or different, R 1 is C 1 -C 4 alkylene, and R 2 is C 1 -C 8 alkyl, allyl, phenyl or phenyl substituted with methyl and / or chlorine, or a metal complex of the imidazole derivative. 2. A composition according to claim 1, wherein the active ingredient is a compound of the above formula (I) in which it is Y is R1-O-R2, n is 1 or 2, X is a chlorine atom, a bromine atom, a methyl group, a nitro group or a trifluoromethyl group, and when n has the value 2, the individual substituents within the meaning of X may be the same or different, R 1 is C 2 -C 4 alkylene, and R 2 is C 1 -C 4 alkyl, allyl or phenyl, or a metal complex thereof. 3. A composition according to claim 1, wherein the active ingredient is a compound of formula (I) above wherein: Y is R1-O-R2, R 1 represents a methylene group and the remaining general symbols are as in point 1, or a metal complex thereof. 4. A composition according to claim 1, wherein the active ingredient is a compound of formula (Ia): C in which is X1 is chlorine or trifluoromethyl, R 1 is an alkylene group having 1 or 2 carbon atoms, and R 2 is C 2 -C 4 alkyl or allyl, or a metal complex thereof. 5. A composition according to claim 4, wherein the active ingredient is a compound of formula (Ia) in which: R 1 is an alkylene group having 2 carbon atoms, and the remaining general symbols are as in point 4, or a metal complex thereof. 6. A composition according to claim 1, wherein the active ingredient is a compound of the formula or a metal complex thereof. 7. A process according to claim 1, wherein the compound of the formula (II) is EMI3.1 wherein: Hal is a halogen atom, and the remaining general symbols are as in 1, reacted with imtdazole, whereupon the resulting product is optionally converted by treatment with a metal salt into its metal complex. 8. The process of claim 7, wherein the starting materials used are compounds of formula (II) in which Hal is a halogen atom and the remaining general symbols are as in point 2. . 9. The process of claim 7, wherein the starting materials used are the compounds of formula (II) in which Hal is a halogen atom, and the remaining general symbols have the meaning as in point á. 10. A process according to claim 7, wherein the compounds of formula (II) in which Hal is a halogen atom are used as starting materials and the remaining general symbols are as defined above. in point 4. 11. The process of claim 7 wherein the starting materials used are compounds of formula (II) in which Hal is an halogen atom and the remaining general symbols are as defined above. as in point 5. 12. The method of claim 7, wherein the starting materials are compounds of the formula Hal represents a halogen atom.