GB1591212A - 1-(n-phenyl-2-alkylimidoyl) imidazole compounds and their use in fungicides - 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

(54)1- [N-PHENYL-2 ALKYLIMIDOYLz IMIDAZOLE COMPOUNDS AND THEIR USE IN FUNGICIDES (71) We, NIPPON SODA COMPANY, LIMITED, of No. 2-i, Ohtemachi 2-chome, Chiyoda-ku, Tokyo, Japan, a company organized under the laws of Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to an imidazole derivative and metal complexes thereof, a process for the preparation thereof and their uses as fungicides, in particular to a fungicidally active composition and method for controlling fungi.

Japanese published patent application No. 39674/77 discloses that some imidazole derivatives have fungicidal activity. The imidazole derivatives are indicated by the general formula

wherein R' is alkyl, Xis halogen, nitro, lower alkyl or lower alkoxy, and n is 0, 1 or 2.

It is also disclosed in the Japanese published patent application No. 46071/77 that some other imidazole derivatives have fungicidal activity. Those imidazole derivatives are shown by the general formula

wherein X" is methyl, chlorine, bromine, nitro or trifluoromethyl, and n is 1 or 2.

Although these known imidazole derivatives have fungicidal activity, the activity is not sufficient and they cause phyto-toxicity to plants. Therefore, these known compounds cannot be put to practical use as fungicides.

According to the present invention there is provided an imidazole compound having the general formula

wherein each X is a substituent individually chosen from a halogen, lower alkyl (C 1-3), nitro or lower haloalkyl (C 1-3); n is 1 or 2; Y is alkoxy (Cl-8)alkyl (C 1-6), lower alkenyloxy (C24)alkyl (C 1-6), phenoxyalkyl (C 1-6), substituted phenoxyalkyl (Cl-6) or a benzyl group, with the proviso that if Y is benzyl, Xn is trifluoromethyl at the 2-position and chlorine at the 4-position.

Preferably each X is a substituent chosen from a halogen, a methyl, a nitro, and trifluoromethyl group, Y is a benzyl or the group having the general formula -R1OR2, R, being an alkylene having 1 to 4 carbon atoms and R2 being an alkyl of 1 to 8 carbon atoms, an alkyl, a phenyl or a phenyl substituted with a methyl group or chlorine.

Advantageously, Y is a benzyl group.

The present invention also extends to metal complexes of the above imidazole compounds. Such metal complexes have outstanding fungicidal activity and cause no phyto-toxicity to plants.

Preferred compounds as fungicides are the compounds of the formula

and metal complexes thereof, and the compounds of the general formula

wherein X1 is chlorine or trifluoromethyl, RX is ylene of 1 to 2 carbon atoms such as methylene, methylmethylene and ethylene, R2 is alkyl of 2 to 4 carbon atoms or allyl and metal complexes thereof.

The compound can be prepared by the reaction shown as follows:

("Hal" represents halogen.) The reaction is carried out in an inert solvent in the presence of an alkaline condensing agent such as sodium carbonate, potassium carbonate, sodium hydroxide, sodium methylalcoholate, trimethylamine, triethylamine, pyridine or piperidine. As an inert solvent, chloroform, dichloromethane, benzene, toluene, xylene, chlorobenzene, acetonitrile, acetone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide or dioxane may be used. Ordinarily, a temperature from the range of OOC to the boiling point of the reaction solution, preferably a temperature from 40"C to the boiling point, is satisfactory. The reaction is usually completed in 1 to 3 hours. After completion of the reaction, the reaction solution is washed with water and dried. The washing and drying may be carried out after replacing the solvent, if necessary. Then the solvent is distilled to obtain the desired compound.

Metal complexes can be prepared by the reaction shown as follows:

(AB is an organic or inorganic metal salt, A is bivalent or trivalent metal atom, B is anion component of the salt and I corresponds to a number of valence of metal atom "A" in the metal salt "AB.") As the metal salt, chloride, sulfate, nitrate or acetate of copper, zinc, nickel, cobalt, manganese, iron or silver is used. Copper sulfate, copper chloride, zinc chloride or zinc acetate is preferably used. When carrying out the reaction for the preparation of the metal complexes the imidazole derivative is dissolved in an inert solvent and a metal salt is added thereto and the mixture is stirred to allow to react. The reaction is ordinarily carried out at room temperature for several minutes. As an inert solvent, any solvents which dissolve the imidazole derivative and are miscible with water can be used. Ordinarily, ethyl acetate, methanol, acetonitrile, dioxane or tetrahydrofuran is used. After completion of the reaction, the reaction mixture is poured into n-hexane or water and the precipitated product is removed by filtration to obtain the metal complex.

The following are examples of preparation of compounds according to the invention.

Example 1.

1 [N2bromophenyl)-2-ethoxypropanimidoyli-imidazole (Compound No. 3) 11 g of 2'-bromo-2-(ethoxy)propionanilide were allowed to react with 8.4 g of phosphorus pentachloride in 50 ml of chloroform by heating the solution under reflux for 30 minutes. Then, chloroform and phosphorus oxychloride formed as by product were removed by distillation and'the residue was dissolved in 40 ml of acetonitrile. To the solution were added 2.8 g of imidazole and 4.1 g of triethylamine and then, the mixture was heated under reflux for 3 hours. After completion of the reaction, acetonitrile was distilled off and the residue was dissolved in 30 ml of dichloromethane. The solution was washed with water several times and dried over anhydrous magnesium sulfate. After distillation of dichloromethane, the residual oil product was purified by silicagel chromatography with dichloromethane to yield 4 g of the desired compound.

(nD 1.5870) Example 2.

1 -[N-(2A-dichlorophenyl)-2-propoxypropammidoyl]imidazole (Compound No. 9) 7.5 g of 2',4'-dichloro-2-(propoxy)propionanilide were allowed to react with 5.6 g of phosphorous pentachloride in 40 ml of chloroform by heating the solution under reflux for 30 minutes. Then, chloroform and phosphorus oxychloride formed as a by-product were removed by distillation under reduced pressure and the residue was dissolved in 40 ml of acetonitrile. To the solution were added 1.9 g of imidazole and 2.7 g of triethylamine and the mixture were heated under reflux for 3 hours. After completion of the reaction, the reaction solution was treated as in Example 1, and 4 g of the desired compound were obtained (n2DI.5690) Example 3.

1 -[N-(4-chloro-2-trifluoromethylphenyl)-2-allyloxypropanimidoyliimidazole (Compound No. 11) 9.3 g of 4'-chloro-2'-trifluoromethyl-2-(allyloxy)propionanilide were allowed to react with 6.3 g of phosphorus pentachloride in 40 ml of chloroform by heating the solution under reflux for 30 minutes. Then, chloroform and phosphorus oxy chloride were removed by distillation and the residue was dissolved in 40 ml of -acetonitrile. To the solution were added 2.1 g of imidazole and 3 g of triethylamine and then the mixture was heated under reflux for 3 hours. After completion of the reaction the reaction solution was treated as in Example 1, and 5 g of the desired compound were obtained. (n2D 1.5440) Example 4.

tN(2,4dichlorophenyl)-2butoxypropanimidoyllimidaz0le (Compound No. 19) 8.8 g of 2',4'-dichloro-2-(butoxy)propionanilide were allowed to react with 6.4 g of phosphorus pentachloride in 40 ml of chloroform by heating the solution under reflux for 30 minutes. Then, chloroform and phosphorus oxychloride were removed by distillation and the residue was dissolved in 40 ml of acetonitrile. To the solution were added 2.1 g of imidazole and 3 g of triethylamine and then, the mixture was heated under reflux for 3 hours. After completion of the reaction, the same treatment as in Example I was carried out to yield 4.5 g of the desired compound.

(n256 1.5682) Example 5.

I -[N-(2,4-dichlorophenyl)-3-propoxypropanimidoyll.imidazole (Compound No.

36) 6.9 g of 2',4'-dichloro-3-(propoxy)propionanilide and 8 g of triethylamine were dissolved in 30 ml of chloroform and 3.7 g of phosgene were introduced thereto at 0 to 100C under cooling with ice. After raising the temperature of the solution to room temperature, the solution was stirred for 2 hours, and then, 2 g of imidazole were added thereto. The mixture was heated under reflux for 2 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature, washed with water and dried over anhydrous magnesium sulfate.

Removal of chloroform from the solution by distillation gave 7.7 g of the desired compound. (n2D 1.5688) Example 6.

I -(N-(4-chlor-2-trifluoromethylphenyl).2-propoxyacetimidoyll-imidazole (Compound No. 37) 12.6 g of 4'-chloro-2'-trifluoromethyl-2-(propoxy)acetanilide and 12.9 g of triethylamine were dissolved in 80 ml of chloroform, and the solution of 6.4 g of phosgene in 30 ml of chloroform was added dropwise thereto.

The solution was stirred for one hour at room temperature, and then, after adding 4.4 g of imidazole thereto, the mixture was stirred fro 15 hours at room temperature. After completion of the reaction, chloroform was removed by distillation. The resulting residue was dissolved in n-hexane, and the solution was washed with water and dried over anhydrous magnesium sulfate. After removal of n-hexane by distillation, the residue was purified by silicagel chromatography to yield 9.8 g of the desired compound. (n23D 1.5370) Example 7.

I [N-(4-chloro-2trifluoromethylphenyl)-sec-butoxyacetamidoyliimidazole (Compound No. 39) 7 g of 4'-chloro-2'-trifluoromethyl-sec-butoxyacetanilide were allowed to react with 5.2 g of phosphorus pentachloride in 50 ml of benzene by heating the solution under reflux for one hour. Then, benzene and phosphorus oxychloride were removed by distillation under reduced pressure and the residual oily product was dissolved in 50 ml of chloroform. To the solution were added 1.7 g of imidazole and triethylamine and then, the mixture was heated for one hour at 500C with stirring.

After stirring the solution for one hour at room temperature, 2.9 g of dried and chloroform was removed by distillation. The residue was purified by silicagel chromatography to yield 1.85 g of the desired compound. (n2D 1.5378) Example 8.

1- - [N-(4-chloro-2-trifluoromethylphenyl)2ethoxyacetimidoyll-imidazole (Compound No. 40) 10 g of 4'-chloro-2'-trifluoromethyl-2-(ethoxy)acetanilide and 10.8 g of triethylamine were dissolved in 80 ml of chloroform, and the solution of 5.3 g of phosgene in 30 ml of chloroform was added dropwise thereto.

After stirring the solution for one hour at room temperature, 2.9 g of imidazole were added thereto and the mixture was stirred for 15 hours at room temperature. After completion of the reaction, chloroform was removed by distillation and the residue was dissolved in n-hexane. The solution was washed with water and dried over anhydrous magnesium sulfate. Removal of n-hexane from the solution by distillation gave 10.2 g of the desired compound (m.p.

49--52"C) Example 9.

I - [N-(2,4-dichlorophenyl)-4-chloro-2-methylphenoxyacetimidoyl] imidazole (Compound No. 43) 3.4 g of 2', 4'-dichloro-(4-chloro-2-methylphenoxy)acetanilide were allowed to react with 2.3 g of phosphorus pentachloride in 40 ml of benzene by heating the solution under reflux for one hour. Then, benzene and phosphorus oxychloride were removed by distillation under reduced pressure and the residual oily product was dissolved in 40 ml of chloroform. To the solution were added 0.75 of imidazole and 1.1 g of triethylamine and the mixture was stirred for one hour at 50 C. After completion of the reaction, the same treatment as in Example 7 was carried out to yield 1.1 g of crystal of the desired compound. (m.p. 84--86"C) Example 10.

1 -[N-(4-chloro-2-trifluoromethylphenyl)-3- imidazole (Compound No. 46) 6.5 g of 4,-chloro-2'-trifluoromethyl-2-(ethoxy)propionanilide were allowed to react with 4.9 g of phosphorus pentachloride in 30 ml of chloroform under reflux for one hour. Then, chloroform and phosphorus oxychloride were removed by distillation under reduced pressure. To the residue were added 3.2 g of imidazole and 30 ml of acetonitrile, and the mixture was heated for 30 minutes under refiux.

After completion of the reaction, acetonitrile was removed by distillation and the residue was dissolved in dichloromethane. The solution was washed with water and dried over anhydrous magnesium sulfate.. After removal of the solvent from the solution by distillation, the residue was purified by alumina column chromatography to yield 3.5 g of the desired compound. (m.p. 61-20C) Example 11.

1 -[N-(4-chloro-2-trifluoromethylphenyl).phenylacetimidoyl] imidazole (Compound No. 56) 3.5 g of N-(4-chloro-2-trifluoromethylphenyl)-phenylacetamide were allowed to react with 2.6 g of phosphorus pentachloride in 40 ml of benzene by refluxing the mixture. After completion of the reaction, benzene and phosphorus oxychloride were evaporated. The resulting N-(4-chloro-2-trifluoromethylphenyl)-phenylacetimidoyl chloride was dissolved in 50 ml of acetonitrile and 0.85 g of imidazole were added thereto with stirring.

To the resulting solution were gradually added 1.3 g of triethylamine with cooling and the solution was maintained for 30 minutes at 60"C. After removal of acetonitrile by distillation, the residue was dissolved in 60 ml of dichloromethane and the solution was washed with water and then dried. An oily product obtained by distillation of dichloromethane from the solution was purified by silicagel column chromatography to obtain 2.1 g of the desired compound. (n2D 1.5818) Example 12.

Bis[l - (N - (2,4 - dichlorophenyl) - 2 - propoxypropanimidoyl) - imidazolejeopper chloride (Compound No. 57) 1 g of l-(N-(2,4-dichlorophenyl)-2-propoxypropanimidoyll-imidazole was dissolved in 5 ml of methanol and 0.5 g -of anhydrous copper chloride were added thereto. The mixture was stirred for 5 minutes at room temperature and then, poured into 100 ml of water to precipitate crystal. Separated crystal by filtration was washed with water and then with n-hexane. The crystal was dried under reduced pressure to yield 1 g of the desired complex (m.p. 165--169"C).

Example 13.

Bis[l - iN - 2,4 - dichlorophenyl) - 2 - propoxypropanimidoyli - imidazole]zinc chloride (Compound No. 58) The reaction of 2 g of 1-[N-(2,4-dichlorophenyl)-2-propoxypropanimidoyl]- imidazole with 0.5 g of anhydrous zinc chloride was carried out as in Example 12 to give 2 g of the desired complex (m.p. 157--158"C) Example 14.

Bis[l - (N - (4 - chloro - 2 - trifluoromethylphenyl) - phenylacetimidoyl}imidazole] copper chloride (Compound No. 82) The reaction of 2 g of 1-[N-(4-chloro-2-trifluoromethylphenyl)phenyl- acetimidoyl]imidazole with 0.5 g of anhydrous copper chloride was carried out as in Example 12 except using ethyl acetate instead of methanol as a reaction solvent to give 2 g of the desired complex. (m.p. 105-108 C).

Bisil IN - (4 - chloro - 2 - trifluoromethylphenyl) - phenylacetimidoyllimidazole]- copper chloride (Compound No. 82) Examples of compounds are listed in Tables I and 2.

TABLE 1

rn N#ICNy Physical Compound Constant No. Xn Y [m.p.l s 1 2-F CPI-O- 23.5 1 2-F -CH-O-C2H5 n235 1.5585 I D CH3 26 2 2-Br I D 1.6222 C113 3 ,, -CH-O-C2H5 n2D5 1.5870 CH3 21 4 2,4 -CH-O-CH3 nD 1.5800 I 5 ,, CH-O-C2Hs n2D4 1.5833 D CH3 6 2-CF3A-Cl -CH-O-CH2 n21 1.5430 I D C3H7n -CH-O-C2H5 7 ,, -CH-O-C,H, n2D1 1.5340 CH2 8 2,4-Br2 ,, .25 D 1.6090 9 2,4-Cl2 -CH-O-C3H7 n2D5 CH, CH3 10 ,, -CH-O-CH2CH-CH2 n25 1.5705 D CH2 11 2-CF3-4-C1 ,, n22 1.5440 D 12 2-CH3 --CH-O-C,H, n22 1.5620 I D CH3 13 2-NO2 ,, [73-76] 14 2-CF3 " .23.5 D 1.5292 15 2-Br-4No2 ,, [160-161] TABLE 1 (cont.)

m Physical Th Compound Xn Constant No. Xn Y [m.p.] nC 25 5 16 2-C1 -CH-O-C2H,, .25.5 1.5720 CH3 17 2-CF3-4-CI -CH-O-C3H7 25.5 5 1.5300 nD CH2 18 2-Br " 25 5 3 1.5820 25 2,4-1, -CH-O-C,H 5 19 2,4-Cl2 -CH-O-C4H9 1.5682 CH2 20 20 2-CFA-Cl ,, 25 5 nD 1.5295 21 2-Ci-5-CH3 -CH-O-C2H, 25 1.5668 I nD CH2 22 2,4-Cl2 -CH-O-C,HI 27.5 1.5700 C!H3 23 2CF3A-Cl ,, [86-87] 24 2,4-Cl2 -CH-O-C4H91 n2D7.5 1.5684 CH2 25 2-CF3-4-Cl ,, n27,5 1.5275 D 26 3,4-Cl2 -CH-O-C2Hs 28 I "D CH3 27 27 2C2H " 1.5541 28 2-NO2-4-CI ,, n27 1.5959 D 27 29 2-NO2-6-CH3 " nD 1.5799 30 4-Cl 26 30 4-CI CHOC4Hgn n2D6 1.5690 CH3 31 2-C1 -CH-O 'C2 H7n n .5 1.5650 I D CH3 TABLE 1 (cont.)

s HN- n Physical I I I Constant No. 0 Xn Y [m.p.] OC 32 2,4-Cl2 CU04 n24 1.6171 D -CII-O I CH3 33 2-CF3-4-Cl ,, [90-93] 34 -CH-O-CHC,H, n2DO 1.5382 34 ,, I I n2D0 1.5382 CH3 CH2 35 2,4-Cl2 ,, n2D6 1.5692 36 2,4-C1, (CH2)2OC3Hn7 n29 1.5688 D 23.5 37 2-CF34-Cl (CH2O3H1u n D 1.5370 n27 1.5765 38 2,4-Cl2 ,, D 34 39 2-CF3-4-C -CH2-O-CHC2H5 n3D4 D 1.5292 CH3 40 ,, -CH2-O-C2H, [49-52] 41 2,4-Cl2 ,, n21 1.5962 D CH 42 2-CF3-4-CI CH2 0 < Ct n2D0 1.5875 43 2,4-C1, ,, [8446] 20 44 ,, -(C112)2-O-C2H, n D 1.5952 45 2-CF2A-Cl (CH2)2OC2H7n n21 1.5463 D 46 ,, -(CH2)2-O-C2H [61-62] 47 ,, -CH2-O-C4H9 n2D3 1.5369 48 " CH3 n2D2 1.5295 49 2,4-CI2 " n2D2 1.5705 TABLE 1 (cont.)

Physical X, Constant No. Xn Y [m.p.] OC 50 ,, CH2OC4Hn9 n22,5 1.5765 D 51 2-CF3-4-Cl -CH,-O-C, H n22 .5 1.5300 D 52 2,4-Cl2 ,, 22.5 1.5717 nD 53 2-CF34-CI -CH2-O-C3H71 n2D2'5 1.5363 54 2,4-Cl2 ,, [52-531 24 55 2-CF3-4-Cl CH2OC,Hn17 nD 1.5225 56 ,, C1424 n2D8 1.5818 TABLE 2

A (a-,:c3i,X, Y Physical Compound . Constant No. Xn Y AB [m.p.] C 57 2,4-C12 CHOC2H7n CuC1, [165-169] CH2 58 ,, ,, ZnC1, [157-158] 59 ,, ,, CuSO4 [90-94] 60 2-CF3A-Cl ,, ZnC1, [48-53] 61 ,, -CH-O-C2H5 " [71-75] CH3 62 ,, -CH2-O-C2H5 ,, [52-56] 63 ,, ,, CuSO4 [91-94] 64 ,, -(CH2)2-O-C2H5 " [138-141] 65 2-CF3-4-Cl CH2OC4Hn9 ZnC1, [5864] 66 " CH2OC3H7n CuSO4 [77-81] 67 ,, ,, ZnC1, [71-74] 68 ,, CH-O-CHC2Hs CuSO4 [76-78] I I CH2 CH2 69 ,, ,, Zinc12 t6466] 70 2,4-C 12 CH2OC4Hgn CuSO4 [117-120] 71 ,, CH2OC5 HA " [103-108] 72 2-CF3-4-CI -CH2-O-C2H;' ,, [81-86] 73 2,4-CI2 " ,, [132-138] 74 2-CF,4-C1 -CH-O-C5H11 ', [144-151] 75 ,, ,, ZnCl2 [5564] 76 ,, -CH2-O-C2H71 ,, [83-88] 77 2,4-C1, CH2O.CHC2Hn7 CuSO4 [78-80] CH3 78 2-CF3-4-Cl ,, ,, [74-76] TABLE 2 (cont.)

A Physical A ( Constant Compound No. Xn Y AB [m.p.] OC 79 2,4-Cl CHOC2Hn7 Fez1, [50-56] CH2 80 ,, ,, Cu(CH3COO)2 38-141] 81 " ,, Zn(CH3Coo)2 [128-130] 82 2-CFg-4-Cl -ClI2 Curl [105-108] 83 " ,, Zn(cH3coo)2 [42-46] "1" corresponds to a number of valence of metal atom "A" in the metal salt "AB".

In the Tables l and 2, preferable compounds as fungicides are Compound Nos.

9 11, 17, 22, 23 34, 36, 37, 38, 39, 40, 56 and metal complexes thereof such as Compound Nos. 57, 58, 59, 62, 63, 82 and 83.

Most of the metal complexes have superior fungicidal activity and superior residual activity to the corresponding free imidazole derivatives.

As mentioned previously, it has been found that compounds possess fungicidal activity when employed to prevent damage to plants.

Such compounds may control a wide variety of fungus diseases of foliage, fruit, stems and roots of growing plants, without damages to the host.

The many fungi against which such compounds are active may be represented by, but is not intended to be limited to, the following: gray mold, sclerotia rot, damping-off and powdery mildew of vegetables, brown rot of peach, leaf spot of corn, scab of apples and pear, rust of pear, powdery mildew of apple, and rust of cereals; and the compounds are particularly effective against powdery mildew, scab and rust.

It is another advantage that such compounds cause no phyto-toxicity to plants.

A method of controlling fungi includes the employment of a liquid or solid composition containing one or more of the compounds as an active component.

The compound may be used directly without mixing with suitable carrier.

The active ingredient of a fungicidal. composition may be formulated by mixing with suitable carriers in a form generally used in pesticidal compositions, such as wettable powder, emulsifiable concentrate, dust formulation, granular formulation, water soluble powder and aerosol. As solid carriers, bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vermiculite and clay, for example, may be used. As liquid carriers, kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone benzene and water, for example, may be used.

If so desired, a surface active agent may be added in order to give a homogeneous and stable formulation.

Further, in the case of using metal complexes as active ingredients, the mixture of corresponding free imidazole derivative and metal salt may be used instead of the metal complex. Namely, the free imidazole derivative and metal salt such as zinc chloride, copper chloride or copper sulfate may be mixed when formulating the fungicidal composition, or when applying to plants. Furthermore, metal containing pesticides such as mancozeb, oxine-copper or fentin hydroxide may be mixed with the imidazole derivatives same as the above-mentioned metal salt.

The concentration of the active ingredient in the fungicidal composition may vary according to type of formulation, and is for example, 5 to 80 weight percent, preferably 20 to 80 weight percent, in wettable powders; 5 to 70 weight percent, preferably 10 to 50 weight percent, in emulsifiable concentrates; and 0.5 to 20 weight percent, preferably 1 to 10 weight percent, in dust formulations.

A wettable powder or an emulsifiable concentrate containing a quantity of the active compound may be suspended or emulsified in water and then sprayed on the foliage of plants or on the locus to be protected.

Furthermore, the compounds may be used in mixture with other fungicides, insecticides, acaricides and herbicides.

Some non-limiting examples of fungicidal compositions are as follows: Example 15.

Wettable Powder Parts by weight Compound No. 9 40 Diatomaceous earth 53 Higher alkyl sulfate 4 Alkylnaphthalene sulfonic acid 3 These are mixed homogeneously and reduced to fine particles to provide a wettable powder containing 40% of the active ingredient. In use, the powder is diluted to a desired concentration with water and is sprayed as a suspension.

Example 16.

Emulsifiable Concentrate Parts by weight Compound No. 56 30 Xylene 33 Dimethylformamide 30 Polyoxyethylene alkylallylether 7 These are mixed and dissolved to provide an emulsifiable concentrate containing 30% of the active ingredient. In use, the concentrate is diluted to a..

desired concentration with water and then is sprayed as an emulsion.

Example 17.

Dust Formulation Parts by weight Compound No. 62 10 Talc 89 Polyoxyethylene alkylallylether These are mixed homogeneously and reduced to fine particles to provide a dust formulation containing 10% of the active ingredient. In use, the formulation is applied directly.

The fungicidal activity of compounds of this invention is illustrated by the following tests: Test l. Test for Control of Gray Mold of Bean The detached leaves of kidney beans (Phaseolus vulgaris) were immersed for about 30 seconds in an aqueous suspension prepared by diluting a wettable powder to a concentration of 200 ppm of a test compound. After being air-dried, the treated leaves were inoculated with mycelia of Botrytis cinerea and kept at 200C in a moist chamber. Control effect was checked 4 days after inoculation. The results are shown in Table 3.

Test 2. Test for Control of Cucumber Powdery Mildew The leaves of potted cucumber seedlings (variety: Satsukimidori) at 1--2 leaf stage were sprayed with an aqueous suspension (5 ml/pot) prepared by diluting a wettable powder to a concentration of 100 ppm of a test compound. After air-dried, the treated leaves were inoculated with conidia of Sphaerothecafuliginea and kept for 9 days at 250C in a greenhouse. Then, control effect was checked. The results are shown in Table 3.

Test 3. Test for Control of Rhizoctonia Damping-off of Cucumber Cucumber seedlings (variety: Suyo) at the cotyledon stage were treated by injecting an aqueous suspension containing a test compound at 100 ppm into the soil (10 ml/pot with 7 seedlings) after being inoculated with mycelia of Rhizoctonia solani. Control effect was evaluated 4 days after inoculation. The results are shown in Table 3.

TABLE 3

Control Value (%) Compound No. Test 1 Test 2 Test 3 1 99 2 93 84 3 100 97 100 4 100 100 5 100 100 6 100 100 7 100 100 100 8 100 100 9 100 100 100 10 100 95 11 100 100 - 100 12 100 95 13 100 89 14 100 100 100 15 100 95 16 100 95 100 17 100 100 100 18 100 100 100 19 100 95 100 20 100 100 100 21 100 100 86 22 100 100 100 23 100 100 10 0 24 100 100 86 25 10 0 100 100 26 100 TABLE 3 (Continued)

Control Value (g) Compound No. Test 1 Test 2 Test 3 27 100 100 95 28 100 89 29 100 100 30 100 87 36 95 37 93 100 100 38 95 100 100 39 100 100 100 40 95 100 100 41 100 79 :42 90 86 43 95 100 45 100 100 46 100 100 56 100 100 100 57 100 100 100 58 100 100 100 59 100 100 100 60 100 100 100 61 100 100 100 62 100 100 100 63 100 100 100 64 100 100 82 96 100 83 . 100 TABLE 3 (Continued)

Control Value (%) Compound No. Test 1 f Test 2 Test 3 Comparative Compound * 1 63 2 90 3 4 Untreated * Comparative Compound

Japanese published patent application No. 39674/77.

2. Euparen: N'-dichlorofluoromethylthio-N,N-dimethyl-N'-phenylsulfamide.

3. Morestan: 6-methyl-1,3-dithiolo[4,5-b]quinoxalin-2-one.

4. PCNB: Pentachloronitrobenzene.

** Phyto-toxicity was observed.

WHAT WE CLAIM IS: 1. An imidazole compound having the general formula

wherein each X is a substituent individually chosen from a halogen, a lower alkyl (C 1-3), a nitro or a lower haloalkyl (C 1-3), n is one or two, and Y is an alkoxy (C 1-8) lower alkyl (C 1-6), a lower alkenyloxy (C24) alkyl Cl-6), a lower phenoxyalkyl (C 1-6), a substituted lower phenoxyalkyl (C 1-6) or a benzyl group, with the proviso that if Y is a benzyl group, Xn is a trifluoromethyl at the 2-position and chlorine at the 4position.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (17)

**WARNING** start of CLMS field may overlap end of DESC **. TABLE 3 (Continued) Control Value (%) Compound No. Test 1 f Test 2 Test 3 Comparative Compound * 1 63 2 90 3 4 Untreated * Comparative Compound Japanese published patent application No. 39674/77. 2. Euparen: N'-dichlorofluoromethylthio-N,N-dimethyl-N'-phenylsulfamide. 3. Morestan: 6-methyl-1,3-dithiolo[4,5-b]quinoxalin-2-one. 4. PCNB: Pentachloronitrobenzene. ** Phyto-toxicity was observed. WHAT WE CLAIM IS:

1. An imidazole compound having the general formula

wherein each X is a substituent individually chosen from a halogen, a lower alkyl (C 1-3), a nitro or a lower haloalkyl (C 1-3), n is one or two, and Y is an alkoxy (C 1-8) lower alkyl (C 1-6), a lower alkenyloxy (C24) alkyl Cl-6), a lower phenoxyalkyl (C 1-6), a substituted lower phenoxyalkyl (C 1-6) or a benzyl group, with the proviso that if Y is a benzyl group, Xn is a trifluoromethyl at the 2-position and chlorine at the 4position.

2. A compound as claimed in claim l, wherein each X is a substituent chosen.

from a halogen, a methyl, a nitro and a trifluoromethyl group, Y is a benzyl or the group having the general formula -R1OR2, Rl being an alkylene having 1 to 4 carbon atoms and R2 being an alkyl of l to 8 carbon atoms, an allyl, a phenyl or a phenyl substituted with a methyl group or chlorine.

3. A compound as claimed in claim 2, wherein the imidazole compound has the general formula

X1 being a trifluoromethyl or chlorine.

4. A compound as claimed in claim 3, wherein R, is an alkylene having l or 2 carbon atoms and R2 is an alkyl having 2 to 4 carbon atoms or an allyl.

5. A compound as claimed in any one of claims 2 to 4, wherein Y is a benzyl group.

6. A metal complex comprising a compound as claimed in any one of the preceding claims.

7. A metal complex as claimed in claim 6, comprising at least one of copper chloride, copper sulfate, copper acetate, zinc chloride, zinc acetate and ferric chloride.

8. A fungicide, comprising an inert carrier and a fungicidally effective amount of a compound as claimed in any one of claims 1 to 5.

9. A fungicide as claimed in claim 8, comprising a metal complex as claimed in either claim 6 or claim 7.

10. A method of controlling fungi, comprising applying to a region to be protected an effective amount of a compound as claimed in any one of claims 1 to 5.

11. A method of controlling fungi as claimed in claim 10, comprising applying a fungicide as claimed in claim 8.

12. A method of making a compound as claimed in any one of claims 1 to 5, comprising reacting a compound of the formula

with imidazole in an inert solvent in the presence of an alkaline condensing agent wherein each X is a substituent individually chosen from a halogen, a lower alkyl (C 1-3), a nitro and a lower haloalkyl (C 1-3), n is one or two, Y is an alkoxyl (C 1-8) lower alkyl (C1--6), a lower alkenoxy (C24) alkyl (C 1-6), a lower phenoxyalkyl (Cla), a substituted lower phenoxyalkyl (C1--6) or a benzyl group, and Hal is a halogen.

13. An imidazole compound as claimed in claim 1 and substantially as hereinbefore described with reference tod'any one of examples 1 to 14.

14. An imidazole compound as claimed in claim 1 and substantially as.

hereinbefore described with reference to any one of the compounds of table 1.

15. A metal complex as claimed in claim 6 and substantially as hereinbefore described with reference to any one of the complexes of table 2.

16. A fungicide as claimed in claim 8 and substantially as hereinbefore described with reference to any one of examples lS to 17.

17. A method as claimed in claim 12 and substantially as hereinbefore described of making an imidazole compound.