CH636088A5 - Imidazole derivatives and a fungicide containing these compounds - Google Patents

Description

The present invention relates to new imidazole derivatives, a fungicidal composition containing these compounds, 55 a process for the preparation of the new compounds and a process for combating fungi.

Japanese published patent application No. 39 674/77 discloses that some imidazole derivatives have fungicidal activity. The imidazole derivatives are represented by 60 the general formula

N

X'n

65

VR '

specified

wherein R 'is alkyl, X' is halogen, nitro, lower alkyl or lower alkoxy and n is 0.1 or 2.

3rd

636088

Another published Japanese Patent Application No. 46071/77 also discloses that some other imidazole derivatives have fungicidal activity. These imidazole derivatives are represented by the general formula

N ^^ - C.aK

vlt "

X n is shown, where 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 insufficient and they cause phytotoxicity in plants. Therefore, these known compounds cannot be used for practical use as fungicides.

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

/ \ ^ N. N "<

X

(I)

wherein shark is halogen, reacted with imidazole and, if appropriate, compounds obtained are converted into the corresponding salts.

The reaction is preferably carried out in an inert solvent in the presence of an alkaline condensing agent such as sodium carbonate, potassium carbonate, sodium hydroxide, sodium methyl alcoholate, trimethylamine, triethylamine, pyridine or piperidine. Chloroform, dichloromethane, benzene, toluene, io xylene, chlorobenzene, acetonitrile, acetone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or dioxane can be used as the inert solvent. A temperature in the range from 0 ° to the boiling point of the reaction solution, preferably a temperature from 40 ° C to the boiling point, is usually satisfactory. The reaction is usually completed in 1 to 3 hours. After the reaction has ended, the reaction solution can be washed with water and dried. The washing and drying can optionally be carried out after replacing the solvent. Then the solvent is usually distilled off to obtain the desired compound.

The complexes of metal salts can be prepared according to the following reaction equation.

Xn

25th

wherein X is identical or different and is halogen, lower alkyl, nitro or lower haloalkyl, n is 1 or 2 and Y is alkoxy-lower alkyl, lower alkenyloxy-aikyl, lower phenoxyalkyl, substituted lower phenoxyalkyl or benzyl, with the proviso that Xn trifluoromethyl in 2-position and chlorine in 4-position means if Y stands for benzyl and complexes of metal salts have an excellent fungicidal activity and do not cause phytotoxicity in plants.

Compounds of the formula which are preferred as fungicides are compounds of the formula

-a

Xn

FROM

A (N N-

\ v

Xn).

N N-C

S

cf3

Jï- ^ Vci

as well as complexes of metal salts, also the compounds of the general formulas

(AB is an organic or inorganic metal salt, A is 30 a divalent or trivalent metal atom, B is the anion component of the salt and 1 corresponds to the valence number of the metal atom "A" in the metal salt "AB".)

The chloride, sulfate, nitrate or acetate of copper, zinc, nickel, cobalt, manganese, iron or silver is preferably used as the metal salt. Copper sulfate, copper chloride, zinc chloride or zinc acetate are preferably used. If the reaction for the preparation of complexes of metal salts is carried out, the imidazole derivative is preferably dissolved in an inert solvent and a metal salt is added to this; the mixture is usually stirred to allow the reaction. The reaction is usually carried out at room temperature for several minutes. Any solvents which dissolve the imidazole-45 derivative and are miscible with water can be used as the inert solvent.

Usually ethyl acetate, methanol, acetonitrile, dioxane or tetrahydrofuran are used. After completion of the reaction, the reaction mixture is generally poured into n-hexane or water; the precipitated crystals can be removed therefrom by filtration in order to obtain the complexes of metal salts according to the invention.

R1OR2

wherein

X represents chlorine or trifluoromethyl,

Rj alkylene with 1 to 2 carbon atoms, such as methylene,

Methylmethylene and ethylene means

R2 represents alkyl with 2 to 4 carbon atoms or allyl and their complexes of metal salts.

The process for the preparation of the new compounds of the formula I is characterized in that a compound of the formula

55

example 1

l- [N- (2-Bromophenyl) -2-ethoxypropanimidoyl] imidazole (Compound No. 3)

Hal-cr '

: »

'Xn

11 g of 2'-bromo-2- (ethoxy) propionanilide were allowed to react with 8.4 g of phosphorus pentachloride in 50 ml of chloroform while heating the solution under reflux for 30 minutes. Then the chloroform and the phosphorus oxychloride formed as a by-product were removed by distillation and the residue was dissolved in 40 ml of acetonitrile. 2.8 g of imidazole and 4.1 g of triethylamine were added to the solution; The mixture was then refluxed for 3 hours. After the reaction was completed, the acetonitrile was distilled away and the residue was dissolved in 30 ml of dichloromethane. The solution was shared several times

636 088

4th

Washed water and dried over anhydrous magnesium sulfate. After distilling the dichloromethane, the remaining oily product was purified by chromatography on silica gel with dichloromethane to obtain 4 g of the desired compound. (nd25 1.5870).

Example 2

l- [N- (2,4-dichlorophenyl) -2-propoxypropanimidoyl] imidazole (Compound No. 9)

7.5 g of 2 ', 4'-dichloro-2- (propoxy) propionanilide was left with

React 5.6 g of phosphorus pentachloride in 40 ml of chloroform by heating the solution under reflux for 30 minutes. Then the chloroform and the phosphorus oxychloride formed as a by-product were removed by distillation under reduced pressure; the residue was dissolved in 40 ml of acetonitrile. 1.9 g of imidazole and

2.7 g of triethylamine added; the mixture was refluxed for 3 hours. After the completion of the reaction, the reaction solution was treated as in Example 1; 4 g of the desired compound were obtained. (nD25 1.5690, melting point 68-69.5 ° C).

Example 3

1- [N- (4-chloro-2-trifluoromethylphenyl) -2-allyloxypropane-imidoyl] imidazole (Compound No. 11)

9.3 g of 4'-chloro-2'-trifluoromethyl-2- (allyloxy) propionanilide was allowed to react with 6.3 g of phosphorus pentachloride in 40 ml of chloroform while the solution or residue was heated for 30 minutes. Then the chloroform and phosphorus oxychloride were removed by distillation and the residue was dissolved in 40 ml of acetonitrile. 2.1 g of imidazole and 3 g of triethylamine were added to the solution; then the mixture was heated under reflux for 3 hours. After completion of the reaction, the reaction solution was treated as in Example 1; 5 g of the desired compound were obtained. (nd22 1.5440).

Example 4

l- [N- (2,4-dichlorophenyl) -2-butoxypropanimidoyl] imidazole (Compound No. 19)

8.8 g of 2 ', 4'-dichloro-2- (butoxy) propionanilide was allowed to react with 6.4 g of phosphorus pentachloride in 40 ml of chloroform while the solution was heated under reflux for 30 minutes. Then the chloroform and phosphorus oxychloride were removed by distillation and the residue was dissolved in 40 ml of acetonitrile. 2.1 g of imidazole and 3 g of triethylamine were added to the solutions; then the mixture was heated under reflux for 3 hours. After the completion of the reaction, the same treatment as in Example 1 was carried out to obtain 4.5 g of the desired compound. (nd25'5 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 were dissolved in 30 ml of chloroform; 3.7 g of phosgene were introduced therein at 0 to 10 ° C. with ice cooling. After raising the temperature of the solution to room temperature, the solution was stirred for 2 hours; then 2 g of imidazole were added. The mixture was refluxed for 2 hours. After the reaction was completed, the resulting reaction solution was cooled to room temperature, washed with water and dried over anhydrous magnesium sulfate. Removal of the chloroform from the solution by distillation gave 7.7 g of the desired compound. (nD29 1.5688).

5 Example 6

l- [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 were dissolved in 80 ml of chloroform; the solution of 6.4 g phosgene in 30 ml chloroform was added dropwise.

The solution was stirred at room temperature for one hour and then, after adding 4.4 g of 15 imidazole, the mixture was stirred at room temperature for 15 hours. After the completion of the reaction, the chloroform was removed by distillation. The resulting residue was dissolved in n-hexane; the solution was washed with water and dried over anhydrous magnesium 20 sulfate. After removal of the n-hexane by distillation, the residue was purified by chromatography with silica gel, so that 9.8 g of the desired compound were obtained. (nD23'5 1.5379, melting point 66-66.5 ° C).

25 Example 7

l- [N- (4-Chloro-2 ~ trifluoromethylphenyl) sec-butoxyacet imidoyl] imidazole (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 while the solution was heated under reflux for one hour. Then the benzene and phosphorus oxychloride were removed by distillation under reduced pressure, and the remaining oily product was dissolved in 50 ml of 35 chloroform. 1.7 g of imidazole and triethylamine were added to the solution, and the mixture was then heated to 50 ° C. with stirring for one hour.

After the reaction was completed, the solution was washed with water and dried; the chloroform was removed by distillation. The residue was purified by silica gel chromatography to give 1.85 g of the desired compound. (nD21 1.5378).

Example 8

45 l- [N- (4-chloro-2-trifluoromethylphenyl) -2-ethoxyacetimidoyl] 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; The solution of 5.3 g of phosgene in 30 ml of chloroform was added dropwise.

After stirring the solution for 1 hour at room temperature, 2.9 g of imidazole was added and the mixture was stirred for 15 hours at room temperature. After the completion of the reaction, the 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 the n-hexane from solution 60 by distillation gave 10.2 g of the desired compound. (Mp 49-52 ° C).

Example 9

l- [N- (2,4-dichlorophenyl) -4-chloro-2-methylphenoxy-acetimidoyljimidazole (Compound No. 43)

65

3.4 g of 2 ', 4'-dichloro- (4-chloro-2-methylphenoxy) acetanilide was left with 2.3 g of phosphorus pentachloride in 40 ml of benzene

5

636088

react by heating the solution under reflux for one hour. Then the benzene and the phosphorus oxychloride were removed by distillation and reduced pressure; the remaining oily product was dissolved in 40 ml of chloroform. 0.75 g of imidazole and 1.1 g of triethylamine were added to the solution; the mixture was stirred at 50 ° C for one hour. After the reaction was completed, the same treatment as in Example 7 was carried out so that 1.1 g of crystals of the desired compound were obtained. (Mp 84-86 ° C).

Example 10

l- [N- (4-Chloro-2-trifluoromethylphenyl) -3-ethoxypropane-imidoyljimidazole (Compound No. 46)

6.5 g of 4'-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. Then the chloroform and the phosphorus oxychloride were heated by distillation under reduced pressure. 3.2 g of imidazole and 30 ml of acetonitrile were added to the residue; the mixture was refluxed for 30 minutes. After the reaction was complete, the acetonitrile was removed by distillation; 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 column chromatography with alumina to obtain 3.5 g of the desired compound. (Mp 61 to 62 ° C).

Example 11

1- [N- (4 ~ chloro-2-trifluoromethylphenyl) phenylacetimidoyl] imidazole (Compound No. 56)

3.5 g of N- (4-chloro-2-trifluoromethylphenyl) phenylacetamide was allowed to react with 2.6 g of phosphorus pentachloride in 40 ml of benzene while the mixture was heated under reflux. After the reaction was completed, the benzene and phosphorus oxychloride were evaporated. The resulting N- (4-chloro-2-trifluoromethylphenyl) phenylacetimidoyl chloride was dissolved in 50 ml of acetonitrile; 0.85 g of imidazole was added with stirring.

15

1.3 g of triethylamine were gradually added to the resulting solution with cooling; the solution was kept at 60 ° C for 30 minutes. After removal of the acetonitrile by distillation, the residue was dissolved in 60 ml of dichloromethane; the solution was washed with water and then dried. An oily product obtained from the solution by distillation of the dichloromethane was purified by column chromatography with silica gel to obtain 2.1 g of the desired compound. (nD28 1.5818, melting point 79 to 81 ° C).

Example 12

Bis [l- {N- (2,4-dichlorophenyl) -2-propoxypropanimidoyl} imidazole copper chloride (Compound No. 57)

1 g of l- {N- (2,4-dichlorophenyl) -2-propoxypropanimidoyl} imidazole was dissolved in 5 ml of methanol; 0.5 g of anhydrous copper chloride was added. Mixture 20 was stirred at room temperature for 5 minutes and then poured into 100 ml of water to precipitate the crystals. The crystals separated by filtration were washed with water and then n-hexane. The crystals were dried under reduced pressure, so that 25 1 g of the desired complex are obtained. (Mp 165-169 ° C).

Example 13

Bis [l- {N- (2,4-dichlorophenyl) -2-propoxypropanimidoyl} - imidazole zinc chloride (Compound No. 58)

30th

The reaction of 2 g of l- [N- (2,4-dichlorophenyl} -2-prop-oxypropanimidoyl] imidazole with 0.5 g of anhydrous zinc chloride was carried out as in Example 12, so that 2 g of the desired complex are produced. (Mp 157-158 ° C).

35

Example 14

Bis [l- {N- (4-chloro-2-trifluoromethyiphenyl) phenylacet imidoyiyimidazole] copper chloride (Compound No. 82)

40 The reaction of 2 g of l- [N- (4-chloro-21-trifluoromethyl-phenyl) -phenylacetimidoyl] imidazole with 0.5 g of anhydrous copper chloride was carried out as in Example 12, except that ethyl acetate was used as the reaction solvent instead of methanol, so that 2 g of the desired 45 complex are generated. (Mp 105-108 ° C).

The examples of the compounds according to the invention are summarized in Tables 1 and 2.

TABLE 1

Connection no.

N N-c: w

Xn

Xn

Physical constant mp ° C

1

2-F

-ch-o-c2h5

nD23-5 1.5585

ch3

2nd

2-br

-ÇH-0-O

nD26 1.6222

ch3

3rd

»

-ch-o-c2h5

nD25 1.5870

1

ch3

4th

5

6

7

8th

9

10th

11

12

13

14

15

16

17th

18th

19th

20th

21st

22

23

24th

25th

6

TABLE 1 (continued)

/ = \

N N-c '^ y

Xn

Xn

Physical constant mp ° C

2,4-Cl,

-ch-o-ch,

nD21 1.5800

2-CF3-4-CI

2,4-Br2 2,4-Cl2

2-CF3-4-Cl 2-CH3

2-NOz 2-CF3 2-Br-4-N02 2-C1

2-CF3-4-CI

2-Br 2,4-Cl2

2-CF3-4-CI 2-C1-5-CH,

2,4-Cl,

2-CF3-4-CI 2,4-CL

c3h7n

-ch-o-c2h5 ch3

-ch-0-CH3

I.

c3H7 «

-ch-o-c2h5 I

ch3

»

-ch-0-C3H, 11

I.

ch3

-ch-o-qh2ch = ch2

Oh,

-CH-O-CnH,

CH,

-CH-0-C3H7n ch3

-ch-0-c4h3n

I.

ch3

-ch-o-c2h5

ch3

-ch-0-c3h7i

C'H "

-CH-O-CA '

nd24 1.5833

nD21 1.5430

nD21 1.5340

nD25 1.6090

nd25 1.5690, 68-69.5 ° C

nd25 1.5705

nD22 1.5440 nD22 1.5620

[73-76] nD23-5 1.5292 [160-161]

Up 1, J 25.5

nD25> 5 1.5300

nd25'5 1.5820

nd25,5 1.5682

nd25'5 1.5295

nD25 1.5668

nd27'5 1.5700

[86-87]

nd27'5 1.5684

CH3

2-CF3-4-CI

nD27'5 1.5275

26

27th

28

29

30th

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

7

TABLE 1 (continued)

636088

N N-C ^

y

Xn

Xn

Physical constant mp ° C

3,4-CL

-ch-o-c2h5

nD28 1.5782

2-C2H5 2-N02-4-Cl 2-N02-6-CH3 4-C1

CH,

-ch-0-c4h9n nD27 1.5541

nD27 1.5959

nD27 1.5799

nD26 1.5690

2-C1 2,4-C12

2-CF3-4-CI

-ch-0-c3h7n

CH,

-ch-o-chc2h5

nD31'5 1.5650 nD24 1.6171

[90-93] nD20 1.5382

ch3 ch3

2,4-Cl2

2,4-Cl2

2-CF3-4-Cl

2,4-Cl2

2-CF3-4-C1

ch2) 2-0-c3h7n ch2-0-c3h7n

-CHo-O-CHCoEL

nD26 1.5692 nD29 1.5688

23.5

1.5379, 66-66.5 ° C 1.5765 1.5292

2,4-Cl2

2-CF3-4-Cl

2,4-Cl2 2-CF3-4-Cl

2,4-Cl2

2-CF3-4-Cl

2,4-Cl2

2-CF3-4-CI

2,4-Cl2

2-CF3-4-Cl ch3

-ch2-o-c2h5

-ch2-O ^ CJI

- (ch2) 2-o-c2h5

- (ch2) 2-0-c3h7n - (ch2) 2-0-c2h5 -ch2-0-c4h9n -ch2-0-ch-c3h, n

I.

CH,

-ch2-o-c4h9 °

-ch2-0-c5hun

-CH.-O-CsH, '»

-ch2-o-c8h17a

[49-52] nD21 1.5962

nD20 1.5875

[84-86]

20th

-CH2-0

nD20 1.5952 nD21 1.5463 [61-62] nD23 1.5369 nD23 1.5295

nD22 1.5705 nD22'5 1.5765 nD22'5 1.5300 nD22-5 1.5717 nD22'5 1.5363 [52-53]

nd24 1.5225

nD28 1.5818, 79-81 ° C

636 088

8th

table 2

Connection no.

W) £ -B

*

Physical constant [mp] ° C

Xn

Y

FROM

57

2,4-Cl2

-ch-0-c3h7n ch3

CuCl2

[165-169]

58

»

»

ZnCl2

[157-158]

59

»

»

CuS04

[90-94]

60

2-CF3-4-CI

»

ZnCl2

[48-53]

61

»

-ch-o-c2h5 oh3

»

[71-75]

62

»

-ch2-0-c2h5

»

[52-56]

63

»

»

CuS04

[91-94]

64

s>

- (ch2) 2-0-c2h5

»

[138-141]

65

2-CFs-4-Cl

-ch2-0-c4h9n

ZnCl2

[58-64]

66

»

-ch ^ o-csh ^

CuS04

[77-81]

67

»

»

ZnCl2

[71-74]

68

»

-ch-o-chc2h5

1 1 -ch3 ch3

CuS04

[76-78]

69

»

»

ZnCl2

[64-66]

70

2,4-CI2

-CH2-0-C4H9n

CuS04

[117-120]

71

»

-CH2-0-C5Hnn

»

[103-108]

72

2-CF3-4-CI

-ch ^ o-cjh /

[81-86]

73

2,4-Cl2

s>

[132-138]

74

2-CF3-4-CI

-CH2-0-C5Hun

»

[144-151]

75

»

»

ZnCl2

[55-64]

76

»

-CH2-0-C3H7i s>

[83-88]

77

2,4-CI2

-CH2-0-CH-C3H7n

1

Oh s

CuS04

[78-80]

78

2-CF3-4-CI

2>

»

[74-76]

79

2,4-Cl

-CH-0-C3H7n ch3

FeClj

[50-56]

80

»

»

Cu (CH3COO) 2

[138-141]

81

»

»

Zn (CH3COO) 2

[128-130]

82

2-CF3-4-CI

-CH2 "0

CuCl2

[105-108]

83

»

»

Zn (CH3CQO) 2

[42-46]

“1” corresponds to the number of valence of the metal atom “A” in the metal salt “AB”

9

636 088

In Tables 1 and 2, the preferred compounds as fungicides are compounds Nos. 9, 11, 17, 22, 23, 34, 36, 37, 38, 39, 40, 56 and their complexes of metal salts e.g. of compounds Nos. 57, 58, 59, 62, 63, 82 and 83.

Most complexes of metal salts have superior fungicidal activity and superior residual activity compared to the corresponding free imid-azole derivatives.

As previously mentioned, it has been found that the compounds of the invention have fungicidal activity when used to prevent damage to plants.

Such compounds can combat a wide variety of fungal diseases of the foliage, fruits, stems and roots of growing plants without harming the host plant.

The many fungi against which such compounds are active are described below, but the scope is not intended to be restricted thereby:

Gray rot, sclerotic rust, rotting and powdery mildew of vegetables, brown rot of peaches, leaf spots of corn, scab of apples and pears, rust of pears, powdery mildew of apples and rust of cereals; the compounds are particularly effective against powdery mildew, scab and rust.

Another advantage of these compounds is that they do not cause phytotoxicity to plants.

The method according to the invention for combating fungi usually comprises the use of a liquid or solid composition containing one or more new compounds of the formula I as the active component.

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

The active component of a fungicidal composition can be formulated by mixing with suitable carriers, as with the pesticidal compositions; Examples of suitable carriers are wettable powders, emulsifiable concentrates, dust formulations, granular formulations, water-soluble powders and aerosols. As solid supports e.g. Bentonite, diatomaceous earth,

Apatite, gypsum, talc, pyrophyllite, vermiculite and clay can be used. Kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, benzene and water can be used as the liquid carrier. If desired, a surfactant can be added to give a homogeneous and stable formulation.

Furthermore, in the case where the complexes of metal salts according to the invention are used as active components, the mixture of the corresponding

free imidazole derivative and the metal salt can be used instead of the complexes of metal salts. This is because the free imidazole derivative and metal salt such as zinc chloride, copper chloride or copper sulfate can be mixed when the fungicidal composition is formulated or when applied to plants. In addition, metal-containing pesticides such as mancozeb, oxy-copper or fentin hydroxide can be mixed with the imidazole derivatives in the same way as the above-mentioned metal salts.

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

A wettable powder or emulsifiable concentrate containing an amount of the active compound can be suspended or emulsified in water and then sprayed onto the foliage of plants or the place to be protected.

In addition, the compounds can be used in a mixture with other fungicides, insecticides, acaricides and herbicides.

Some non-limiting examples of fungicidal compositions of the invention are the following:

Example 15 Wettable powder

Parts by weight

Compound No. 9 40

Diatomaceous earth 53

higher alkyl sulfate 4

Alkylnaphthalenesulfonic acid 3

These are mixed homogeneously and crushed into fine particles in order to sweep a wettable powder with a content of 40 percent of active component. In use, the powder is diluted with water to the desired concentration and sprayed as a suspension.

Example 16 Emulsifiable concentrate

Parts by weight

Compound No. 56 30

Xylene 33

Dimethylformamide 30

Polyoxyethylene alkyl allyl ether 7

These are mixed and dissolved to produce an emulsifiable concentrate with a 30% active component. In use, the concentrate is diluted to the desired concentration with water and then sprayed as an emulsion.

Example 17 Dust formulation

Parts by weight

Compound No. 62 10

Talk 89

Polyoxyethylene alkyl allyl ether 1

These are mixed homogeneously and crushed into fine particles to form a dust formulation containing

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

636088

10th

generate 10% of active component. When used, the formulation is applied directly.

The fungicidal activity of the compounds according to the invention is explained using the following tests:

Test 1. Test for the control of gray rot of beans

The loosened leaves of make-up beans (Phaseolus vulgaris) were immersed for about 30 seconds in an aqueous suspension which was prepared by diluting a wettable powder to a concentration and 200 ppm of a test compound. After air drying, the treated leaves were inoculated with botrytis cinerea mycelia and kept in a humid chamber at 20 ° C. The control effect was tested 4 days after the inoculation. The results are shown in Table 3.

Test. 2. Test for the control of powdery mildew of cucumbers The leaves in pots of seedlings (type: Satsuk-imidori) at the 1-2 leaf stage were washed with an aqueous suspension (5 ml / pot), which was diluted up to a wettable powder a concentration of 100 ppm of a test compound was sprayed. After air drying, the treated leaves were inoculated with Conidia from Sphaerotheca fuliginea and kept in a greenhouse at 25 ° C for 9 days. Then the control effects were examined. The results are shown in Table 3.

Test 3. Test for controlling cucumber decay by Rhizoctonia cucumber seedlings (species: Suyo) in 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 them with my-

TABLE 3 (continued)

celien from Rhizoctonia solani. The control effect was evaluated 4 days after the Einimp-fund. The results are shown in Table 3.

TABLE 3

Connection no.

Control value (%) Test 1 Test 2

Test 3

1

99

2nd

93

84

3rd

100

97

100

4th

100

100

5

100

100

6

100

100

7

100

100

100

8th

100

100

9

100

100

100

10th

100

95

11

100

100

100

12

100

95

13

100

89

Connection no.

Test 1

Control value (%) test 2

Testing

14

100

100

100

15

100

95

io16

100

95

100

17th

100

100

100

18th

100

100

100

15 19

100

95

100

20th

100

100

100

21st

100

100

86

20 22

100

100

100

23

100

100

100

24th

100

100

86

25 25

100

100

100

26

100

27th

100

100

95

30 28

100

89

29

100

100

30th

100

87

35 36

95

37

93

100

100

38

95

100

100

40 39

100

100

100

40

95

100

100

41

100

79

45 42

90

86

43

95

100

45

100

100

50 46

100

100

56

100

100

100

57

100

100

100

58

55

100

100

100

59

100

100

100

60

100

100

100

61

100

100

100

60

62

100

100

100

63

100

100

100

64

100

100

65

82

96

100

83

100

TABLE 3 (continued)

Connection control value (%)

Test 1 Test 2 Test 3

Comparative compound

1 63 0 **

2 90

3 90

4 90

Untreated 0 0 0

* Comparison connection,

CH3

/ C = \ published, unchecked

1. N. N-CT Japanese patent application

1ÇH-CH2CH2CH3 No. 39 674/77

CH3

2. Euparen: N'-dichlorofluoromethylthio-N.N-dimethyl-N'-phenyl-

sulfamide

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

4. PCNB: pentachloronitrobenzene

** Phytotoxicity has been observed.

Claims (18)

636088 2nd PATENT CLAIMS 1. Compounds of general formula I \ y Xn (I) wherein X is the same or different and is halogen, lower alkyl, nitro or lower haloalkyl, n is 1 or 2 and Y is alkoxy-lower alkyl, lower alkenyloxy-alkyl, lower phenoxyalkyl, substituted lower phenoxyalkyl or benzyl, with the proviso that Xn trifluoromethyl in 2-position and chlorine in the 4-position means if Y is benzyl and complexes of metal salts. 2. Compounds according to claim 1, characterized in that X is the same or different and means halogen, methyl, nitro or trifluoromethyl; Y represents either benzyl or the group of the formula -RjORa, in which Rj denotes alkyl having 1 to 4 carbon atoms, allyl, phenyl or phenyl substituted by methyl and / or chlorine. 3. Compound of the formula Xv G- < ^ Ri-0- wherein Xj is trifluoromethyl or chlorine as a compound according to claim 2. 4. A compound according to claim 3, characterized in that R! represents alkylene having 1 to 2 carbon atoms and R 2 is alkyl having 2 to 4 carbon atoms or allyl. 5. A compound according to claim 2, characterized in that Y is benzyl. 6. A compound according to claim 1, characterized in that the complexes of metal salts of the imidazole compound are selected from the group consisting of copper chloride, copper sulfate, copper acetate, zinc chloride, zinc acetate and iron (III) chloride. 7. Fungicidal agent, characterized in that a new compound of the formula I as at least one active ingredient Xn indicates that it contains an inert carrier and a fungicidally effective amount of a compound according to claim 6. 13. A method for combating fungi, characterized in that a compound of the formula I is used. 5 turns. 14. A method for combating fungi according to claim 13, characterized in that an effective amount of a compound according to claim 2 is applied to the location to be protected. 15. A method for combating fungi according to claim 13, characterized in that an effective amount of a compound according to claim 3 is applied to the location to be protected. 16. A method of combating fungi according to anise spoke 13, characterized in that an effective amount of a compound according to claim 4 is applied to the place to be protected. 17. A method of combating fungi according to claim 13, characterized in that the to 20 protective site applies an effective amount of a compound according to claim 5. 18. A method of combating fungi as claimed in claim 13, characterized in that an effective amount of a compound is applied to the site to be protected. 25 applies according to claim 6. 19. Process for the preparation of new compounds of general formula I. 30th rv Xn (I) wherein X is the same or different and represents halogen, lower alkyl, nitro or lower haloalkyl, n is 35 1 or 2 and Y is alkoxy lower alkyl, lower alkenyloxy alkyl, lower phenoxyalkyl, substituted lower phenoxyalkyl or benzyl, with the proviso that Xn trifluoromethyl in the 2-position and chlorine in the 4-position means, if Y stands for benzyl and complexes of metal salts, characterized in that a compound of the formula Kal-C Xn (I) 45 wherein X is identical or different and is halogen, lower alkyl, nitro or lower haloalkyl, n is 1 or 2 and Y is alkoxy-lower alkyl, lower alkenyloxy-alkyl, lower phenoxyalkyl, substituted lower phenoxyalkyl or benzyl, with the proviso that Xn trifluoromethyl in 2-position and chlorine in the 4-position means if Y is benzyl and contains complexes of metal salts. 8. Fungicidal composition according to claim 7, characterized in that it contains an inert carrier and a fungicidally effective amount of a compound according to claim 2. 9. Fungicidal composition according to claim 7, characterized in that it contains an inert carrier and a fungicidally effective amount of a compound according to claim 3. 10. Fungicidal composition according to claim 7, characterized in that it contains an inert carrier and a fungicidally effective amount of a compound according to claim 4. 11. Fungicidal composition according to claim 7, characterized in that it contains an inert carrier and a fungicidally effective amount of a compound according to claim 5. 12. Fungicidal composition according to claim 7, characterized wherein shark is halogen, reacted with imidazole and, if appropriate, compounds obtained are converted into the corresponding salts. 50