DK157490B - IMIDAZOLE COMPOUNDS, FUNGICIDE PRODUCTS WITH CONTENTS AND PROCEDURES TO COMBAT FUNGI - Google Patents

Description

in

DK 157490 B

The present invention relates to novel imidazole compounds and metal complexes thereof, a fungicidal product and a method for controlling fungi.

5 Japanese Patent Publication No. 39674/77 states that some imidazole derivatives have a fungicidal effect. The imidazole derivatives are represented by the general formula 1. X = N-cf '- ^ X' wherein R 'is alkyl, X' is halogen, nitro, lower alkyl or lower alkoxy and n is 0, 1 or 2.

15 Japanese Publication No. 46071/77 also states that some other imidazole derivatives have a fungicidal effect. These imidazole derivatives are shown by the general formula 20 wherein X "is methyl, chloro, bromo, nitro or triflourmethyl and n is 1 or 2.

Although these known imidazole derivatives have a fungicidal effect, the effect is not sufficient and they are phytotoxic to 30 plants. Therefore, these known compounds cannot in practice be used as fungicides.

It has been found that the aforementioned novel imidazole compounds have the general formula 35

DK 157490 B

2. Wherein Y is the same or different substituents selected from the group consisting of halogen, (C3-3) alkyl, nitro and (C1-3) haloalkyl, n is one or two and Y is selected from the group; consisting of (C1-8) alkoxy (C1-6) alkyl / (C2-4) alkenyl-oxy (C2-6) alkyl, (C7_13) phenoxyalkyl, methyl- or chlorine-substituted (C7_3) phenoxyalkyl and benzyl, with the proviso that Xn is trifluoromethyl at the 2-position and chlorine at the 4-position when Y is benzyl, and metal complexes of the imidazole compounds of the formula "~ Ά

A (N H-C 2 ·, · B)

where A is a bivalent or trivalent metal atom, B is an anion component of the salt and S corresponds to the valence number of A in salt AB, has excellent fungicidal activity and is not phytotoxic to plants.

Preferred compounds as fungicides are the compound of formula <X 2 and metal complexes thereof, and compounds of general formula 35

DK 157490 B

Wherein Τ is chlorine or trifluoromethyl, R 1 is lower alkylene of 1-2 carbon atoms such as methylene, methyl methylene and ethylene, R 2 is lower alkyl of 2-4 carbon atoms or allyl, and 10 metal complexes thereof.

The compounds of the present invention may be prepared by the reaction shown in the following: "S xn + + + xn 20 (" 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 methyl alcohol, tri methyl ami η, triethyl ami η, pyridine or piperidine. As an inert solvent can be used chloroform, dichloromethane, benzene, toluene, xylene, chlorobenzene, acetonitrile, acetone, dimethylsulfoxide, tetrahydrofuran, dimethyl formamide or dioxane. A temperature in the range of 0 ° C to the boiling point of the reaction solution, preferably a temperature of 40 ° C to the boiling point, is generally satisfactory. The reaction is usually completed after 1 to 3 hours. After completion of the reaction, the reaction solution is washed with water and dried. Washing and drying can be carried out after replacing the solvent if necessary. The solvent is then distilled to obtain the desired compound.

DK 157490 B

4

A starting material for the compounds of the invention may e.g. is prepared by the reaction shown below: xn *. rf “5 Xn 'ΐ ^ Λ-ΝΚ + YC-OH ---> YCONII - /" ^ - ^ VHal-C * \ _ / * O'

Y

Metal complexes of the present invention can be prepared by the following reaction

Nn + AB ^ A (N Vc ^ 15 Y * (AB is an organic or inorganic metal salt, A is a bivalent or trivalent metal atom, B is an anion component of the salt, and in 20 corresponds to a number of valences of metal atom "A" in the metal salt "AB").

As the metal salt, the 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 are preferably used. When the reaction is carried out to prepare 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 reaction. The reaction is usually carried out at room temperature for several minutes. As such inert solvent can be used any such solvents which dissolve the imidazole derivative and are miscible with water.

Ethyl acetate, methanol, acetonitrile dioxane or tetrahydrofuran are commonly used. 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 present invention.

DK 157490 B

5

Most of the metal complexes have better fungicidal activity and better residual action than the corresponding free imidazole derivatives. The residual effect here is understood to be synonymous with "sustained efficacy in the control of plant diseases".

5

As previously mentioned, it has been found that the compounds of the present invention have a fungicidal effect when used to prevent plant damage.

10 Such compounds can fight a wide variety of fungal diseases of leaves, fruits, stems and roots of growing plants without damaging the host.

The many fungi against which such compounds are effective can be represented by the following:

Gray mold, sclerotia tips, black legs and powdery mildew in vegetables, brown advice in pears, leaf spot in corn, scab in apples and pears, rust in pears, powdery mildew in apples and rust in 20 grains, and the compounds are particularly effective against powdery mildew, scab and rust.

It is also an advantage of such compounds that they are not phytotoxic to the plants.

25

The fungicidal product of the invention is characterized by the characterizing part of claim 2.

The process of the present invention is characterized by the characterizing part of claim 3 and comprises the use of a liquid or solid product containing one or more of the compounds of the invention as an active component.

The compound can be used directly without mixing with a suitable carrier.

The active ingredient in a fungicidal product of the invention may e.g. prepared by mixing with suitable carriers in a 6

DK 157490B

form commonly used for pesticidal products such as a wettable powder, emulsifiable concentrate, powder, granular product, water-soluble powder and aerosol. As fixed carriers lean e.g. apply bentonite, diatomaceous earth, apatite, plaster, talc, pyrophyllite, vermiculite and clay. As liquid carriers e.g. used are kerosene, mineral oil, petroleum, extraction gasoline, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, benzene and water. If desired, a surfactant may be added to form a homogeneous and stable product.

In addition, in the case of using metal complexes of the invention 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, can be mixed by preparation of the fungicidal product or by application to the plants. Metal-containing pesticides such as mancozeb, oxine copper or fetine hydroxide can also be mixed with the imidazole derivatives, as is the metal salt mentioned above.

The concentration of the active ingredient in the fungicidal product may vary by product type and is e.g. 5-80% by weight, preferably 20-80% by weight, in wettable powders, 5-70% by weight, preferably 10-50% by weight, in emulsifiable concentrates and 0.5-20% by weight, preferably 1-10% by weight. % in powders.

A wettable powder or emulsifiable concentrate containing a portion of active compound can be suspended or emulsified in water and then sprayed onto the leaves of the plants or site to be protected.

The compounds can also be used in admixture with other fungicides, insecticides, acaricides and herbicides.

The following Examples 1-14 illustrate the preparation of compounds of the present invention.

35 7

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Example 1.

1- / N- (2-bromophenyl) -2-ethoxypropanimidoyl7-imidazole (Compound No. 3) 11 g of 2, -bromo-2- (ethoxy) propionanilide was allowed to react with 8.4 g of phosphorus pentachloride in 50 ml of chloroform at heating the solution at reflux for 30 minutes. Chloroform and phosphorus oxychloride formed as a by-product were then removed by distillation and the residue was dissolved in 40 ml of acetonitrile. To the solution was 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 is washed with water several times and dried over anhydrous magnesium sulfate. After distillation of dichloromethane, the oil residue was purified by silica gel = 15 chromatography with dichloromethane to give 4 g of the desired compound. (njp = 1.5870).

Example 2.

1- / N- (2,4-Dichlorophenyl) -2-propoxypropanimidoyl7-imidazole (Compound No. 9) 7.5 g of 2 ', 4'-dichloro-2- (propoxy) propionanilide was allowed to react with 5.6 of phosphorus pentachloride in 40 ml of chloroform by heating the solution at reflux for 30 minutes. Chloroform and phosphorus oxychloride formed as a by-product were then removed by distillation under reduced pressure, and the residue was dissolved in 40 ml of acetonitrile. To the solution was added 1.9 g of imidazole and 2.7 g of triethylamine, and the mixture was heated under reflux for 3 hours. Upon completion of the reaction, the reaction solution was treated as set forth in Example 1 and 4 g of the desired compound were obtained. fSmp. 68-69.5 ° C).

Example 3

1- [β- (4-Chloro-2-trifluoromethylphenyl) -2-allyloxypropanimidoyl7-imida2 (Compound No. 11)

DK 157490 B

8 9.3 g of 4, -chloro-2'-trifluoromethyl-2- (allyloxy) propionanilide were allowed to react with 6.5 g of phosphorus pentachloride in 40 ml of chloroform by heating the solution under reflux for 30 minutes. Chloroform and phosphorus oxychloride were then removed by distillation and the residue was dissolved in 40 ml of acetonitrile. To the solution was added 2.1 g of imidazole and 3 g of triethylamine, and then the mixture was heated under reflux for 3 hours. Upon completion of the reaction, the reaction solution was treated as in Example 1 and 5 g of the desired compound was obtained.

10 ("d5 = i-s") ·

Example 4

1- / N- (2,4-dichlorophenyl) -2-butoxypropanimidoyl7-imidazole (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 at reflux for 30 minutes. Chloroform and phosphorus oxychloride were then removed by distillation and the residue was dissolved in 40 ml of acetonitrile. To the solution was added 2.1 g of imidazole and 3 g of triethylamine, and the mixture was then heated under reflux for 3 hours. Upon completion of the reaction, the same treatment as set forth in Example 1 was carried out to prepare 4.5 g of the desired compound (n

Example 5

1-β- (2,4-dichlorophenyl) -3-propoxypropanimidoyl7-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 was added at 0 to 10 ° C 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 was added thereto. The mixture was refluxed 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. (n ^ p = l, 5688).

9

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Example 6

1- [4- (4-DiLoro-2-trifluoromethylphenyl) -2-propoxyacetimidoyl7-imidazole (Compound No. 37) 12.6 g of 4'-chloro-2'-trifluoromethyl-2- (propoxy) acetanilide and 12.9 g 5 triethylamine was dissolved in 80 ml of chloroform and the solution of 6.4 g of phosgene in 30 ml of chloroform was added thereto.

The solution was stirred for 1 hour at room temperature and after addition of 4.4 g of imidazole, the mixture was stirred for 15 hours at room temperature. After completion of the reaction, chloroform was removed by distillation. The residue obtained was dissolved in n-hexane and the solution washed with water and dried over anhydrous magnesium sulfate. After removal of n-hexane by distillation, the residue was purified by silica gel chromatography to obtain 9.8 g of the desired compound. (Sap. 66-66.5 ° C)

Example 7

L / N- (4-chloro-2-trifluoromethylphenyl) -sec-butoxyacetimidoyl7imidazo! (Compound No. 39) 20 g of 4'-chloro-2'-trifluoromethyl-sec-butoxyacetanilide was allowed to react with 5.2 g of phosphorus pentachloride in 50 ml of benzene on heating, at reflux for one hour. Benzene and phosphorus oxychloride were then removed by distillation under reduced pressure and the residual oily product was dissolved in 50 ml of chloroform. To the solution was added 1.7 g of imidazole and triethylamine, and the mixture was then heated for 1 hour at 50 ° C. stirring.

After completion of the reaction, the solution was washed with water and dried, and chloroform was removed by distillation. The residue was purified by silica gel chromatography to give 1.85 g of the desired compound, (n + 1 = 1.5378).

Example 8.

1- / N- (4-chloro-2-trifluoromethylphenyl) -2-ethoxyacetimidoyl7-imidazole (Compound No. 40) 35 g of 4'-chloro-2'-trifluoromethyl-2- (ethoxy) acetanilide and 10 g. 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 thereto.

DK 157490B

10

After stirring the solution for one hour at room temperature, 2.9 g of imidazole was added and the mixture was stirred for 15 hours at room temperature. Upon completion of the reaction, chloroform was removed by distillation and the residue was dissolved in n-hexane. The solution 5 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

1- / N- (2,4-dichlorophenyl) -4-chloro-2-methylphenoxyacetymidoyl / imidazole (Compound No. 43) 3.4 g of 2,4,4-dichloro- (4-chloro-2-methylphenoxy) acetanilide was allowed to react with 2.3 g of phosphorus pentachloride in 40 ml of benzene by heating the solution at reflux for 1 hour. Benzene 15 and phosphorus oxychloride were then removed by distillation under reduced pressure and the residual oily product dissolved in 40 ml of chloroform. To the solution was added 0.75 g of imidazole and 1.1 g of triethylamine, and the mixture was stirred for 1 hour at 50 ° C. Upon completion of the reaction, the same treatment as in Example 7 was carried out to prepare 1.1 g of crystals of the desired compound. (Mp 84-86 ° C).

Example 10.

1- / N- (4-chloro-2-trifluoromethylphenyl) -3-ethoxypropanimidoyl7imidazole (Compound No. 46) 6.5 g of 4i-chloro-2, trifluoromethyl-2- (ethoxy) propionanilide was allowed to react with 4, 9 g of phosphorus pentachloride in 30 ml of chloroform under reflux for one hour. Chloroform and phosphorus oxychloride.

was then removed by distillation under reduced pressure. To the residue was added 3.2 g of imidazole and 30 ml of acetonitrile, and the mixture was heated at reflux for 30 minutes. Upon 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 removing the solvent from the solution by distillation, the residue was purified by alumina column chromatography to obtain 3.5 g of the desired compound c (S.p. 61-620 ° C).

Example 11.

11

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1- / N- (4-chloro-2-trifluoromethylphenyl) -phenylacetirnidoyl] 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 at reflux of the mixture. After the reaction was complete, 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 was added thereto with stirring.

10

To the resulting solution, 1.3 g of triethylamine was gradually added under cooling and the solution was kept at 60 ° C for 30 minutes. After removing 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 silica gel column chromatography to obtain 2.1 g of the desired compound ... (mp 79-81 ° C).

Example 12.

2 0

Bis / l- / N- (2,4-dichlorophenyl) -2-propoxypropanimidoyl} -imidazoic copper chloride (Compound nh 57) 1 g of 1- {N- (2,4-dichlorophenyl) -2-propoxypropanimidoyl} -imidazole was dissolved in 5 ml of methanol and 0.5 g of anhydrous copper chloride was added. The mixture was stirred for 5 minutes at room temperature and then poured into 100 ml of water to precipitate crystals. Pre-filtered crystals were washed with distilled water and then with n-hexane. The crystals were dried under reduced pressure to prepare 30 g of the desired complex (mp 165-169 ° C).

Example 13

Bis./I-{N-2,4- dichlorophenyl) -2- propoxypropanimidoyl} -imidazole7 ~ 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 indicated in Example 12 to prepare 2 g of the desired complex. (Mp 157-158 ° C),

Example 14.

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Bis / 1- (n- (4-chloro-2-trifluoromethylphenyl) -phenylacetimidoyl} -imidazolyl) copper chloride (Compound No. 82)

The reaction of 2 g of 1- / N- (4-chloro-2-trifluoromethylphenyl) -phenyl-acetimidoyl-7-imidazole with 0.5 g of anhydrous copper chloride was carried out as indicated in Example 12, except that ethyl acetate was used instead of ethyl acetate. methanol as the reaction agent 10 to prepare the desired complex (mp 105-108 ° C),

Examples of compounds of the present invention are given in Tables 1 and 2.

15 20 25 30 35

Table 1

13 DK 157490 B

γ Physically

Connection __ Constant

Clock. Yn (melting point) ° C.

1 2-F -CH-0-C2H5 n'2D'5 1 »5585 iH3 2 2-B'r -CH-0 - ^% n2 ^ 1.6222 5 3» -CH-0-C2H5 n2 ^ 1, 5870

CEL

5

4 2,4-ClO -CH-O-CEL

2 i 3 21 C- ^ Hy ^ 1,5800 5 »-CH-O-C2H5 n2 ^ 1,5833 ch3 6 2-CF, -4-Cl -CH-O-CIL n2 ^ 1.5430

2 I -n J

C3H7 7 »-CH-O-C2H5 h2J 1.5340 ch3 8 2.4-Br2 n25 1 6090

9 2,4-Cl2 -CH-O-C3Hy Mp. 68-69.5 ° C

ch3 10 "-CH-O-CH2CH = CH2 n2p 1.5705 CH, 5 11 2-CF3-4-Cl" n22 1.5440 12 2-CH3 -CH-O-C2H5 n22 1.5620 feH3 13 2-NO0 "/ 73-767 14 2-CF3" n2 ^ '5 1.5292 15 2-Br-4-NO2 "/ 160-1617 16 2-C1" n25'5 i, 5720 x D ___

j __ “_ pc .4-5.74.9.0 B

. 17 2-CF3-4-Cl -CR-O-C ^ n25 ^ 5 1.5300

CHX

3 18 2-Br "n23 ^ 3 1> 5 & 20 · JL9 2,4-Cl2 -CH-QC ^ Hg n23 ^ 3 1,5682 ch3 20 2-CF3-4-Cl» n23 ^ 3 1 '5295 21 2- Cl-5-CH3 -CH-O-C2H5 η23 1,5ββ8 4¾ 22 2,4-Cl2 -CH-O-C

CHX

5 23 2-CFx-4-Cl 2 / 86-877 5 "24 2.4-03-2 -CH-O-C ^ Hg n27 ^ 5 1.5684 ch3 25 2-CFx-4-Cl" n27, 1.5275

0 D

26 3.4-01, -ΟΗ-Ο-Ο, Η, - n28 1.5782

43 D

27 2 ~ C2H5 "n27 1» 5541 28 2-NO2-4-Cl "n27 1.5959 29 2-NO2-6-CH3" n27 1.5799 30 4-01 -CH-OC ^ Hg n28 1.5690 ch3 31 2-C1 - (jJH-OC ^ n31 £ 5 1.3830 ch3 32 2 s 4-01 ~ 0Η-0 = £ ^ n24 1.6171 ch3 33 2-CF3-4-Cl "/ 90-937 j 34 »-CH-0-CHC2Hp; n20 1,5.382 | chx 6ή-," i

3 3 I

15 DK 157490 B

2,4-Cl 2 -CH-O- (J: HC 2 B 5 n 2 1.5692 3 36 36 2,4-Cl 2 - (CH 2) 2-O-C

37 2-CF3-4-Cl -CH2-0-C3Hy Mp. 66-66r5 ° C

38 2,4-Cl2 "n2 1.5765 39 2-CP3-4-Cl -CH2 O-CHCl3 n3 ^ 1.5292 CH, 40" -CH2-O-C2H5 / 49-527 41 2, 4-Cl2 "n2 1.5962 CH3 \ 42 2-CF3-4-Cl-O2-O2-01 n2 ° 1.5875 43 2,4-Cl2" / 84-867 44 "- (CH2) 2-0-C2H5 n2 ° 1.5952 45 2-CF3-4-Cl - (CH2) 2-0-C3H ^ n22 1.5463 46 "- (CH2) 2-0-C2H3 / 51-62? 47 "-CH2-O-C4Hg te23 1.5369 48" -CHo-O-CH ~ C

2 I 3 7 D

ch3 LS 99 2,4-Cl2 Ώβ 1,5705 "-CH2-O-C4Hg n22 £ J 1.5765 2-CF3-4-Cl" CH2 "°" C5Hii n22 ^ '1,5300 2,4-Cl2 « n22? 5 1.5717 2-CF, -4-Cl -CHo-O-C ^ Hi n22? 5 1.5365.

5) | ^ 'D

16 DK 157490 B

54 2,4-Cl2 -CH2-O-C3H ^ / 52-537 55 2-CF3-4-Cl -CH2-O-C8H ^ 7 n2 £ 1,5225

56 ° -CH2 ^ Srnp 79-81 ° C

17 DK 157490B

Table 2.

H- (Qj-Xn *

Fortin- A (VC \ Y 4'B Physical Sharing ___ Constant

per. Xn Ύ AB (melting point) ° C

57 57 2,4-Cl 2 -CH-OC CuCl2 / 165-1697 ch3 58 »" ZnCl2 / 157-158 / 59 "" CuS04 / 90-947 60 2-CF3-4-Cl 11 ZnCl2 / 48-537 61 51 -CH-0-C2H5 »/ 71-757 ch3 62 11 -CH2-0-C2H5" / 52-567 63 "" CuSO4 / 91-947 I'64 "- (CH2) 2-0-C2H5" / 138- 1417 65 2-CF3-4-Cl -CH2-0-C4Hg ZnCl2 / 58-647 66 "-CH2-0-C3H ^ CuS ° 4 / 77- = 817 67" "ZnCl2 /" 71-747 68 "-CH -0-CHC2H5 CuSO4 / 76-78 /

CEU CEU

2 5 -69 "" ZnCl2 / 54-667 70 2,4-ci2 -ch2-o-c4h "j CuSO4 / 117-1207 71", -CH2-0-C5H "1 I" / 103-1087 i 72 2 ~ CFj-4-Cl - -CH2-0-0jHy j »/ 81-867

18 DK 157490 B

73 2,4-Cl2 -CH2-O-C3H ^ CuSO4 / 132-1387 74 2-CF3-4-Cl -CH2 OC3 "/ 144-1517 75" "ZnCl2 / 55-647 76" -CH2- 0-C3H2 "/ 83-887 77 2,4-Cl2 -CH2-O'CH-C3H2 CuSO4 / 78-807 in3 78 2-CF2 -4-Cl" "/ 74-767 79 2.4- Cl -CH-O-C3H ^ FeCl3 / 50-567 80 "" Cu (CH3C00> 2 / 138-1417 81 "" Zn (CH3C00) 2 / 128-1307 82 2-CF3-4-Cl -CH2 ^ 3 CuCl2 "J" corresponds to a number of valences of metal atom "A" in the metal salt "AB".

19

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In Tables 1 and 2, preferred fungicidal compounds are compounds Nos. 9, 11, 17, 22, 23, 34, 36, 37, 38, 39, 40, 56 and metal complexes thereof, such as Nos. 57, 58, 59, 62 , 63, 82 and 83.

5

Some examples of fungicidal products of the invention are listed below;

Example 15

10

Removable powder Weight parts

Compound No. 9 48 15 Diatomaceous earth 53 Higher alkyl sulfate 4

Alkylnaphthalene sulfonic acid 3

These are homogeneously mixed and reduced to fine particles to produce a wettable powder containing 40¾ of the active ingredient. In use, the powder is diluted to a desired concentration with water and sprayed as a suspension.

Example 16.

25

Emulsifiable concentrate Weight parts

Compound No. 56 30

Xylene 33

Dimethylformamide 30 Polyoxyethylene alkyl allyl ether 7

These are mixed and dissolved to prepare an emulsifiable concentrate containing 30% of the active ingredient in a brew, the concentrate is diluted to a desired concentration and then sprayed as an emulsion.

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Example 17

20

Powder Weight parts

Compound No. 62 10 5 Talc 89

Polyoxyethylene alkyl allyl ether 1

These are homogeneously mixed and reduced to a fine particle size to produce a powder containing 10% of the active ingredient. In use, the product is applied directly.

The fungicidal action of the compounds of the invention is illustrated by the following experiments: Experiment 1.

Tests for controlling gray mold on bean.

The affected garden bean leaves (Phaseolus vulgaris) were dipped for approx. 30 seconds in an aqueous suspension prepared by diluting a wettable powder to a concentration of 200 parts per minute. million of a test compound After air drying, the treated leaves were seeded with mycelium of Botrytis cineria and kept at 20 ° C in a humid room. The effect was checked 4 days 25 after inoculation. The results are shown in Table 3.

The control value is calculated as follows: average lesion diameter of treated (1 _ -) x 100 average of lesion diameter of untreated) 35

....... 21 DK 157490 B

Experiment 2.

Cucumber Powder Powder Test Tests 5 Leaves on cucumber seedlings in pot (variety: Satsukimidori) at the 1-2 leaf stage were sprayed with an aqueous suspension (5 ml / pot) prepared by diluting a wettable powder to a concentration of 100 parts per ml. million of a test compound. After air drying, the treated leaves were seeded with cones of Sphaerotheca fuliginea and kept for nine days at 25 ° C in the greenhouse. The control effect was then examined. The results are shown in Table 3.

The disease severity is recorded using the following indices.

15 0 (healthy) 0.5 fewer than 4 injuries per leaf 1 infection less than 10% of leaf 2 infection less than 25% 20 3 infection less than 50% 4 infection more than 51%

The control value is calculated as follows: 25 (i - sum of indices on treated y x j0o sum of indices on untreated 30 35

Experiment 3.

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Cucumber seedlings (variety: Suyo) at the seedling stage were treated by injecting an aqueous suspension containing a test compound at a concentration of 100 parts per gram. million in soil (10 ml / pot with 7 seedlings) after inoculation with mycelia of Rhizoctonia solani. The control effect was assessed 4 days after inoculation. The results are shown in Table 3.

The control value is calculated as follows: (1- number of healthy plants on treated) x and increase the number of healthy plants on untreated 15 20 25 30 35. . . 23 \

Table 3.

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Connection Control value (%) number ____, __

Experiment 1 Experiment 2 Experiment 3 1 99 2 93 84 3 100 97 100 4 100 100 5 100 100 6 100 100

7 1QQ 1QQ 1QQ

8 1Q0 1Q0 9 100 1Q0 100 10 100 95 11 10Q 100 10 Q.

12 1Q0 95 13 100 89.

14 1QQ 1QQ 100 15 10 Q 95 16 10Q 95 100 17 100 100 100 18 100 100 100 19 100 95 1Q0 20 100 100 100 21 100 100 86 22 100 100 100 23 100 1Q0 100 24 100 100 86 25 100 100 100 26 100 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 24

Table 3 (continued)

Compound ____ Campaign value (%) .______

«I

Experiment 1 Experiment 2 Experiment 3_ 40 95 100 1Q0 41 100 79 42 90 86

43 95 1QQ

45 100 100 46 100 100

56 100 100 10Q

57 100 100 100 58 100 100 100

59 100 100 10Q

60 100 100 100 61 100 100 1Q0

62 100 100 10Q

63 100 100 100 64 100 100

82 96 10Q

83 100

Comparative Compound x 1 63 0 xx 2 90 3 90 4 Untreated 0 0 0 x Comparison Compound CH ^ f = \ sO * 1. n r Japanese Patent Application no.

CH CH2CH2CH3 39674/77

Ch3 1 2

Euparen: N'-dichlorofluoromethylthio-N / N-dimethyl-N'-phenylsulfamide.

2

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

Claims (3)

4. PCNB: Pentachlorine nitrobenzene. ** Phytotoxicity was found. 5 Patent claims. An imidazole compound to be used as a fungicide, characterized in that it is selected from the group consisting of (a) imidazole compounds of the general formula V / Y in which X is the same or different substituents selected from the group; consisting of halogen, (C1-3) alkyl, nitro and (C1-3) haloalkyl, n is one or two and Y is selected from the group consisting of (C1-8) alkoxy (C1-6) alkyl, (C2-4) alkenyl -oxy (C2-g) alkyl, (C7..13) phenoxyalkyl, methyl- or chloro-substituted (C7-13) phenoxyalkyl and benzyl, with the proviso that Xn is trifluoromethyl in 2-step 11 and chloro in 4- when Y is benzyl, and (b) metal complexes of the imidazole compounds of (a) of Form-1 an "x / Y" where A is a bivalent or trivalent metal atom, B is an anion component of the salt and S corresponds to the valence number of A in salt AB. 2. A fungicidal product, characterized in that it comprises an inactive carrier and at least one compound according to claim 1. Method for controlling fungi, characterized in that an effective amount of a compound according to claim 1 or a product according to claim 2 is added to the site to be protected.