CS203192B2 - Fungicide and method of producing its active components - Google Patents

Abstract

Cyclopropanecarboxanilides have the following formula <IMAGE> in which R1 is hydrogen or C1-C4-alkyl, R2 denotes an aromatic hydrocarbon radical or an aromatic hydrocarbon radical which is substituted one or more times by identical or different substituents comprising C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, nitro, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl and/or cyano, and n denotes the number 1 or 2. The compounds of the formula I are prepared by reacting a cyclopropanecarbonyl chloride with an appropriate 3-anilino-2-perhydrofuran. Fungicides contain, as the active component, at least one new compound of the formula I.

Description

The present invention relates to novel fungicidal compositions containing novel compounds, such as cyclopropanecarboxylic acid anilides, for combating phytopathogenic fungi, and to a process for the preparation of novel compounds which form the active ingredients of these fungicidal compositions.

Compositions having activity against phytopathogenic fungi are already known. Means of this type known in the art are, for example

5-ethoxy-3-trichloromethyl-1,2,4-thldiazole (U.S. Patent Nos. 3,260,588 and 3,260,725) and tetramethylthiouram disulfide (German Patent No. 642,532). However, these compositions do not always have a satisfactory effect against phytopathogenic fungi.

It is an object of the present invention to provide a composition having an excellent action against phytopathogenic fungi.

This object is achieved according to the invention by a fungicidal composition which comprises at least one cyclopropanecarboxylic acid anilide of the formula I as active ingredient.

where

R 1 represents a hydrogen atom or a C 1 -C 1 alkyl group,

R 6 is an aromatic C 6 hydrocarbon residue or once or twice, the same or differently

C 1 -C 1 -alkyl,

C 1 to C 1 -alkoxy,

C 1 -C 6 -alkylthio, halogen, trifluoromethyl, nitro,

C 1 -C 6 -alkoxycarbonyl,

And C1 denotes the numbers 1 to 2, optionally in admixture with carriers and / or auxiliaries.

The fungicidal composition according to the invention preferably contains as an active ingredient at least one of the following compounds of formula I:

Cyclopropanecarboxylic acid [N- (2-oxoperhydro-3-furyl) anilide], Cyclopropanecarboxylic acid [2,6-diethyl-N- (2-oxoperhydro-3-furyl) anilide], [2-methoxy] - N- (2-oxoperhydro-3-furyl janilide) cyclopropanecarboxylic acid,

Cyclopropanecarboxylic acid 2,6-dimethyl-N- (2-oxoperhydro-3-furyl) anilide, [4-methyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [2,4- cyclopropanecarboxylic acid dimethyl N- (2-oxoperhydro-3-furyl) anilide, cyclopropanecarboxylic acid [3-chloro-N- (2-oxoperhydro-3-furyl) anilide], [3-fluoro-N- ( 2-oxoperhydro-3-furyl] anilide.] Cyclopropanecarboxylic acid, [3-bromo-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [2,6-diisopropyl-N- (2-oxoperhydro- 3-furyl Janilide] cyclopropanecarboxylic acid, [2-ethyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [4-ethyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid Cyclopropanecarboxylic acid [4-fluoro-N- (2-oxoperhydro-3-fluoro) anilide], cyclopropanecarboxylic acid [2-ethoxy-N- (2-oxoperhydro-3-furyl) anilide], [3-chloro- Cyclopropanecarboxylic acid 2-methyl-N- (2-oxoperhydro-3-furyl) anilide, [ 3-chloro-N- (5-methyl-2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [3'-ethyl-N- (2-oxoperhydro-3-furyl janilide) cyclopropanecarboxylic acid, [3- cyclopropanecarboxylic acid cyano-N- (2-oxoperhydro-3-furyl) anilide, cyclopropanecarboxylic acid [3-thiomethyl-N- (2-oxoperhydro-3-furyl) anilide], [2,3-dichloro-N- ( 2-Oxoperhydro-3-furyl] -anilide] cyclopropanecarboxylic acid.

Process for the preparation of the active ingredients of the fungicidal composition according to the invention, i.e. the novel cyclopropanecarboxylic acid anilides of the general formula

in which

R 1 represents a hydrogen atom or a C 1 -C 6 -alkyl group,

R 2 is an aromatic C 1 -C 4 hydrocarbon radical, or once or twice, equally or differently, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, halogen, trifluoromethyl, nitro, C 1 -C 4 alkoxycarbonyl, C 1 to C4-alkylcarbonyl and / or. According to the present invention, a cyano-substituted C6-hydrocarbon radical an denotes 1 or 2 is characterized in that the compounds of the general formula II (CH 2 CH n -h, ^R t ° (II)

R1, R2 and n are as defined above, reacting with cyclopropanecarboxylic acid chloride of the formula:

ClrC & CHI in the presence of an acid binding agent and optionally a solvent. at a temperature of -10 to + 120 ° C, preferably in equimolar amounts. at a temperature of 0 ° C to. to room temperature, and the reaction products are isolated in a manner known per se.

Surprisingly, the compounds according to the invention outweigh the known compositions of the same type of activity against phytopathogenic fungi and, moreover, are characterized by good plant tolerance and sufficient duration of action. Furthermore, since they are not phytotoxic in amounts which are practically possible, they can therefore be used advantageously in agriculture and horticulture to combat phytopathogenic fungi.

The compounds of the invention have excellent fungicidal properties against harmful fungi such as false powdery mildew.

In contrast to the only prophylactic effect, there are 203192 known fungicidal agents such as N-trichloromethylthiophthalimide (U.S. Pat. Nos. 2,553,770, 2,553,771 and 2,553,776) and manganese ethylene bis-dithiocarbamate (U.S. Pat. Nos. 2,504,404). and 2,710,822) the compounds of the invention surprisingly have the further advantage of a curative and systemic effect and thus permit the control of disease agents already established in plants.

Among the compounds according to the invention, in particular those compounds in the general formula I have an excellent fungicidal action

R1 represents a hydrogen atom, a methyl or ethyl group,

R 2 represents phenyl, methylphenyl, dimethylphenyl, ethylphenyl, isopropylphenyl, methoxyphenyl, ethoxyphenyl, methylthiophenyl, fluorophenyl, chlorophenyl, bromophenyl, dichlorophenyl, trifluoromethylphenyl, nitrophenyl, cyanophenyl, methoxycarbonylphenyl or acetyl;

Either the active ingredient alone or mixtures of at least two structurally different active ingredients from a number of compounds of the invention may be used. If desired, other fungicides, nematicides, herbicides or other pest control agents may be added as desired.

The active compounds are expediently used in the form of preparations such as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents, and optionally wetting agents, adhesives, emulsifying agents and / or dispersing agents.

Suitable liquid carriers are water, mineral oils or other organic solvents such as xylene, chlorobenzene, cyclohexanol, dioxane, acetonitrile, ethyl acetate, dimethylformamide, isophorone and dimethylsulfoxide.

Suitable solid carriers are lime, kaolin, chalk, talc, attaclay and other clays, as well as natural or synthetic silicic acid.

Among the surfactants which may be mentioned are, for example: ligninsulfonic acid salts, alkylated benzenesulfonic acid salts, sulfonic acid amides and their salts, polyethoxylated amines and alcohols.

If the active substances are intended for seed dressing, colorants may also be added to give the seed which has been seeded a clearly visible color.

The proportion of active ingredient (s) in the composition can be varied within wide limits, the exact concentration of active ingredient used in the composition being primarily dependent on the amount in which the composition is to be used, inter alia, for seed or leaf spraying. The compositions contain, for example, between 1 and 80% by weight, preferably between 20 and 50% by weight, of active ingredient and about 99 to 20% by weight of liquid or solid carriers, and optionally up to 20% by weight of surfactants.

As acid binding agents, for example, organic bases such as pyridine, triethylamine or N, N-dimethylaniline or inorganic bases such as hydroxides, oxides and carbonates of alkali metals and alkaline earth metals such as sodium, potassium or calcium may be used.

For example, ether, tetrahydrofuran, benzene, ethyl acetate and others can be used as solvents. Liquid acid-binding agents such as pyridine can be used simultaneously as solvents.

The reaction is conveniently carried out at temperatures of from -10 ° C to 120 ° C.

The following example illustrates the preparation of the compounds of the invention.

Examples

Example 1 Cyclopropanecarboxylic acid [N- (2-oxoperhydro-3-furyl) anilide] (Compound No. 1)

6.30 g (0.06 mol) of cyclopropanecarboxylic acid chloride are added dropwise to a solution of 10.62 g (0.06 mol) of 3-anilino-hydrofuran-2-one in 50 ml of pyridine at an internal temperature of 5 to 10 ° C with stirring . Stirring at room temperature is continued for 0.5 hour, then the reaction mixture is poured into 200 g of ice-water and mixed well. After aspiration, wash thoroughly with water and dry in an oven.

Yield: 10.25 g = 70% of theory, melting point

104 ° C.

The following compounds of the invention may also be prepared analogously:

Compound number _t Name Physical constant (melting point) ° C 2 Cyclopropanecarboxylic acid [2,6-diethyl-N- (2-oxoperhydro-3-furyl) anilide] 102 to 103 3 Cyclopropanecarboxylic acid [2-methoxy-N- (2-oxoperhydro-3-furyl) anilide] 175 to 176 4 - [2-Methyl-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furyl] anilide] 108 to 109 5 Cyclopropanecarboxylic acid [2,6-dimethyl-N- (2-oxoperhydro-3-furyl) anilide] 114 to 116 6 Cyclopropanecarboxylic acid [2,5-dimethyl-N- (2-oxoperhydro-3-furyl) anilide] 84 7 Cyclopropanecarboxylic acid [3-methyl-N- (2-oxoperhydro-3-furyl) anilide] 109 8 Cyclopropanecarboxylic acid [4-methyl-N- (2-oxoperhydro-3-furyl) anilide] 123 9 Cyclopropanecarboxylic acid [3,4-dimethyl-N- (2-oxoperhydro-3-furyl) anilide] 99 to 100 10. Cyclopropanecarboxylic acid [2,3-dimethyl-N- (2-oxoperhydro-3-furyl) anilide] 153 11 Cyclopropanecarboxylic acid [2,4-dimethyl-N- (2-oxoperhydro-3-fluoro) anilide] 85 to 86 12 Cyclopropanecarboxylic acid [3,5-dimethyl-N- (2-oxoperhydro-3-furyl) anilide] 103 13 Cyclopropanecarboxylic acid [2,4,6-trimethyl-N- (2-oxoperhydro-3-furyl) anilide] 119 to 121 14 [4-chloro-N- (2-oxoperhydro- 3-furyl] -anilide] cyclopropanecarboxylic acid 149 to 150 15 Dec [3-chloro-N- (2-oxoperhydro-99-100)] Cyclopropanecarboxylic acid -3-furyl janilide]. 16 Cyclopropanecarboxylic acid [4-isopropyl-N- (2-oxoperhydro-3-furyl) anilide] 108 to 110 17 Cyclopropanecarboxylic acid [3-trifluoromethyl-N- (2-oxoperhydro-3-furyl) anilide] 104 to 105

Compound number Name Physical constant (melting point) ° C 18 (3-Fluoro-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furyl) anilide 89 19 Dec [3-bromo-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furyl) anilide 93 to 94 20 May Cyclopropanecarboxylic acid [2,6-dlisopropyl-N- (2-oxoperhydro-3-furyl) anilide] 215 to 216 21 (2-Ethyl-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furyl) anilide 103 22nd [4-ethyl-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furyl) anilide 107 23 Cyclopropanecarboxylic acid [4-methoxy-N- (2-oxoperhydro-3-furyl) anilide] 75 24 [4-bromo-N- (2-oxoperhydro- 3-furyl) anilide] cyclopropanecarboxylic acid 144 to 145 25 [4-fluoro-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furanililide] 138 to 139 26 Cyclopropanecarboxylic acid [2-ethoxy-N- (2-oxoperhydro-3-furyl) anilide] 143 to 145 27 Mar: [3-chloro-2-methyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid 121 to 124 28 [5-chloro-2-methyl-N- (2-oxoperhydro-3-furanyl) anilide] cyclopropanecarboxylic acid 114 to 116

29 Cyclopropanecarboxylic acid (4-methoxy-2-methyl-N- (2-oxoperhydro-3-furyl) anilide) n _D ²⁰ : 1.5520 30 Cyclopropanecarboxylic acid [4-ethoxy-N- (2-oxoperhydro-3-furyl) anilide] n _D ²⁰ : 1.4579 31 Cyclopropanecarboxylic acid [5-chloro-2-methoxy-N- (2-oxoperhydro-3-furanyl) anilide] 163 to 164 32 Cyclopropanecarboxylic acid [3-chloro-N-5-methyl- (2-oxoperhydro-3-furyl) anilide] 95 to 97 33 [3-ethyl-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furyl) anilide 69 to 70

Compound number Name Physical constant (melting point) ° C 34 [3-cyano-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furyl) anilide 142 to 143 35 Cyclopropanecarboxylic acid [3-thlomethyl-N- (2-oxoperhydro-3-furanyl) anilide] n _D ³⁰ : 1.5888 36 [2,3-dichloro-N- (2-oxoperhydro- Cyclopropanecarboxylic acid -3-furyl) anilide 136 to 137 37 Cyclopropanecarboxylic acid [3-chloro-N- (5-methyl-2-oxoperhydro-3-furyl) anilide] 95 to 97

The compounds according to the invention are usually almost colorless, odorless crystalline substances, which are almost insoluble in water and gasoline, on the other hand being well soluble in polar organic solvents, for example acetone, dimethylformamide and dimethylsulfoxide.

The starting materials for the preparation of the compounds according to the invention are known per se or can be prepared by known methods.

The following examples serve to illustrate the possible uses of the compounds of the invention.

Example 2

Limiting concentration test for controlling Pythium ultimatum% powder formulations of the active ingredients were uniformly mixed with the soil which was heavily infested with Pythium utimatum. The 0.5 liter clay trays were filled with treated soil and 20 grains of 'Wunder von Kelvedon' stamped peas were sown in each dish without a shelf life. After cultivation for 3 weeks at 20-24 ° C, the number of healthy peas was determined and the root quality was evaluated (1-4).

The active substances, the amounts used and the results are shown in the following table.

A compound of the invention Concentration of active substance in mg / l of ground Number of healthy peas Root quality (d-4) [N- (2-oxoperhydro-3-fluoro-) 10 ' 17 4 ry 1) anilide] cyclopropanecar- 20 May 17 4 boxylic acids 40 18 4 [2,6-dimethyl-N- (2-oxo-) 10 16 4 perhydro-3-furyl) anilide] - 20 May 20 May 4 cyclopropanecarboxylic 40 19 Dec 4 acid [3-chloro-N- (2-oxoperhyd- 10 19 Dec 4 trans-3-furyl) anilide] cyclo- 20 May 17 4 propanecarboxylic 40 17 4 acid [3-methyl-N- (2-oxoper- 10 10 1 hydro-3-furyl) anilide] cyclo- 20 May 16 2 propanecarboxylic 40 16 4 acid [2-methoxy-N- (2-oxoper- 10 10 1 Hydro-3-furyl) anilide] cyclo- 20 May 16 2 propanecarboxylic 40 20 May 4

acid

A compound of the invention Concentration of active substance in mg / l of ground Number of healthy peas Quality. roots (1-4) Reference substance 10 2 1 5-Ethoxy-3-trichloro- 20 May 5 1 methyl-1,2,4-thiadiazole 40 12 3 Control (3 '' repetition) and) 1 1 Infested soil (b) 0 - Control Il C) 0 (3 reps) and) 19 Dec 4 Evaporated soil (b) 18 4 C) 18 4

Root quality = white roots without fungal necroses = white roots, slight fungal necroses —brown roots, already strong fungal necroses = strong fungal necroses, rotten roots

Example 3

Pickling diabetes

Calibrated. seed of the sugar beet species. 'Dieckmann-Suprapoly' was stained with a 20% powder formulation of the active substance. Clay dishes for 2 liters of ground (20X20X5 cm) were filled with normal compost soil (damping-off) and 100 ml of sugar seed was sown in each bowl. After a cultivation period of 18 days at 19-21 ° C in a greenhouse, the number of healthy seedlings was determined.

The active substances, the amounts used and the results are shown in the following table.

A compound of the invention Active substance in g / kg of seed Number of healthy seedlings [N- (2-oxoperhydro-3-fluoro-) 0.4 79 ryl) anilide] cyclopropanecar- 0.8 79 boxylic acids 1.6 75 [2,6-dimethyl-N- (2-oxo-) 0.4 70 Perhydro-3-furyl) anilide] - 0.8 76 cyclopropanecarboxylic 1.6 83 acid [3-chloro-N- (2-oxoperhyd- 0.4 83 ro-3-furyl) anilide] cyclo- 0.8 82 propanecarboxylic acids · 1.6 93 (3-Methyl-N- (2-oxoper- 0.4 77 hydro-3-furyl) anilide] cyclo- 0.8 71 propanecarboxylic acids 1.6 85 [2-methoxy-N- (2-oxoper- 0.4 83 hydro-3-furyl) anilide] cyclo- 0.8 87 propanecarboxylic acids 1.6 87 Comparative substances 5-Ethoxy-3-trichloro- 0.4 26 methyl-1,2,4-thiadiazole 0.8 44 1.6 53 tetramethylthiuram- 4.8 21 disulfide 9.6 50 Control (3 reps) and) 5 contaminated soil (b) 7 C) 6

Compound of the Invention Active substance in g / kg of seed Number of healthy seedlings Control · II (3 reps) and) 83 vaporized soil (b) 86 C) 81

Example 4

Effect of prophylactic leaf treatment against Plasmopara viticola on vine plants in greenhouse

Young vine plants with about 5 to 8 leaves were sprinkled with the indicated concentration, after the spray coating had dried, sprayed with an aqueous suspension of fungus sporangia (about · 20,000 per ml) at the bottom of the leaf and immediately incubated in a greenhouse at 22-24 ° C and preferably in an atmosphere saturated with steam.

From the next day, the air humidity was reduced to a normal value (about 30 to 70% saturation) for 3 to 4 days and then maintained for a further one day with steam saturation. Then · the percentage of fungal infested area was recorded on each leaf and the average of each treatment to determine fungicidal activity calculated as follows:

100. ^šetl attack ^{of 10 °,} _d ^{ni, ch} ----- =% efficacy of the untreated

Compounds of the invention ° / on effect against Plasmopare viticola *) Concentration (% active substance) [2,6-dlethyl-N- (2-oxoperhydro-3-furyl) anilide]] cyclopropanecarboxylic acid 40 0,025 [-3-Fluoro-N- (2-oxo-hydrohydro-3-furyl-janilide) -cyclopropanecarboxylic acid 100 ALIGN! 0,025 Cyclopropanecarboxylic acid [3-bromo-N- (2-oxoperhydro-3-furyl) anilide] 100 ALIGN! 0,025 Cyclopropanecarboxylic acid [2,6-diisopropyl-N- (2-oxoperhydro-3-furyl) anilide] 84 0,025 Cyclopropanecarboxylic acid [2-ethyl-N- (2-oxoperhydro-3-furyl) anilide] 83 0,025 Cyclopropanecarboxylic acid [4-ethyl-N- (2-oxoperhydro-3-furyl) anilide] 40 0,025 Cyclopropanecarboxylic acid [4-fluoro-N- (2-oxoperhydro-3-furyl) anilide] 100 ALIGN! 0,025 Cyclopropanecarboxylic acid [2-ethoxy-N- (2-oxoperhydro-3-furyl) anilide] 70 0,025 [3-chloro-2-methyl-N- (2-oxoperhydro-3-furyl) anilide] -cyclopropanecarboxylic acid 98 0,025 Cyclopropanecarboxylic acid [3-ethyl-N- (2-oxoperhydro-3-furyl) anilide] 100 ALIGN! 0,025

13 203192 14 Compounds of the invention % effect against Plasmopare viticola *) Concentration (% active substance) Cyclopropanecarboxylic acid [3-cyano-N- (2-oxoperhydro-3-furyl) anilide] 100 ALIGN! 0,025 Cyclopropanecarboxylic acid [3-thiomethyl-N- (2-oxoperhydro-3-furyl) anilide] 70 0,025 Cyclopropanecarboxylic acid [2,3-dichloro-N- (2-oxoperhylamino-3-furyl) anilide] 100 ALIGN! 0,025 Cyclopropanecarboxylic acid N- (2-oxoperhydro-3-furyl) anilide 100 ALIGN! 0.001 Cyclopropanecarboxylic acid [3-chloro-N- (2-oxoperhydro-3-furyl) anilide] 100 ALIGN! 0.001 *) The effect is related to 100% infestation in the untreated control.

Example 5

Effect of prophylactic treatment of leaves against Phytophtora infestans in tomatoes or potatoes in a greenhouse

Young tomato plants with at least two developed leaves or potato plants (for example, seed seedlings) of at least 10 cm in height were sprinkled with the indicated concentration and after drying, sprayed with an aqueous suspension containing 50,000-80,000 fungal spores per milliliter and incubated for 2 hours in temperature 11 ° C. The plants were incubated with the compounds of the invention. Concentration (% active ingredient) 0.005 was grown at high humidity and at a temperature of about 15-18 ° C in a greenhouse and after about 5 days the percentage of uninfected leaf area was assessed. The fungicidal activity was calculated as follows:

100—

100. infections treated with _n ,

----- 7 - ^ - 3 ------ =% UCinnOStl attack untreated% efficacy against Phytophtora infestans in potatoes *)

Compounds of the invention

Concentration (% of active substance) 0,005 (N- (2-oxoperhydro-3-fu-95-yl) anilide) cyclopropanecarboxylic acid [2,6-dimethyl-N- (2-oxoper-80-hydro-3-furyl) anilide] acid cyclopropanecarboxylic

Comparative substance ethylene bis-dithiocarbamate50 manganese% activity against Phytophtora infestans in tomatoes *) (N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid

Cyclopropanecarboxylic acid [3-methyl-N- (2-oxoperhydro-81-r-3-furyl) anilide] [3-chloro-N- (2-oxoperhydro-91-

Cyclopropanecarboxylic acid -3-furyl) anilide

Reference substance Manganese (ethylene bis-dithiocarbamate 67)

·) The effect is related to 100% infestation in the untreated control

Example 6

Systemic effect of soil treatment against Phytophtora infestans in tomatoes or potatoes in a greenhouse

The weighed substances were mixed with topsoil (weight: volume), the topsoil was filled into pots and planted with young tomato plants with at least two developed leaves or potato plants (for example, seeded seedlings) at least 10 cm high. After the desired normalized time (e.g., 4 or 18 days), the plants were sprayed with an aqueous suspension containing 50,000-80,000 fungus spores per milliliter incubated for about 2 hours in a refrigerator at 11 ° C. The plants were incubated at high atmospheric humidity and at a temperature of about 15 to 18 ° C in a greenhouse and after about 5 days the percentage of infested leaf area was assessed. The fungicidal activity was calculated as follows:

100.napadení

100- ošetiených -----_ _/ v efficacy attacked oeošetřeoých

Systemic effect of soil treatment against Phytophtora infestans in tomato plants (active substance weight: volume)

Compounds of the invention ppm of active ingredient % efficiency *) 4 doy before iooculation treatment 18 days before inoculation [N- (2-oxoperhydro-3-fu- 25 89 85 ryl) anilide] cyclopropanecar- boxylic acids 5 70 89 [2,6-dimethyl-N- (2-oxo-) 25 92 82 perhydro-3-furyl) azilide] - cyclopropanecarboxylic acid 5 40 71

*) The efficacy is based on 100% infestation of the untreated control.

Example 7

Curative effect of leaf treatment against Phytophtora infestans in tomato or potato plants in a greenhouse

Young tomato plants with at least two developed leaves or potato plants (for example of seed seedlings) at least 10 cm tall were. sprayed with an aqueous suspension containing 50,000 to 80,000 spore fungi per milliliter and incubated for about 2 hours in a refrigerator at 11 ° C. The plants were incubated at high humidity. After

Compounds of the invention% sprayed active substance [N- (2-oxsperhydro-3-furyl) -0,004 aoilide] cyclopropaocarboxylic acid [2,6-dimethyl-N- (2-oxo-0,004 perhydro-3-furyl) anilide] cyclopropanecarboxylic acids

Comparative substance 0.004 manganese ethyle-bis-dithiscarbamate expired at the desired standard. Over time, the plants were sprinkled with the tested fungicide concentration during the period of late fungal attack. After the outbreak of fungus infestation. the percentage of infested leaf area was assessed in the treated control plants. The fungicidal effect was calculated as follows:

100. napadení

10 ° ^- · ° ^; ·· ^'0' / _ · _towards ^ink "attacked oeošetřeoých

% effect *) before inoculation at 1 day post-inoculation 100 ALIGN! 68 100 ALIGN! 60 91 0

1S

Example 8

Effect of treatment of barley seeds against Helminthosporum spec.

Barley seeds infested with Helminthosporum spec. Were treated with the active ingredient in an amount of 50 mg per 100 g seeds. Then the seeds were sown in the soil and incubated in a air-conditioning chamber at + 15 ° C. The experiment was evaluated after 6 weeks with seedlings showing a significant reduction in attack compared to the plants of the untreated control group.

Compounds of the Invention% Activity of [4-methyl-N- (2-oxoper-40 hydro-3-furyl) anilide] cyclopropanecarboxylic acid [2,4-dimethyl-N- (2-oxoper-40-hydroxy-3-furanyl)] 1) cyclopropanecarboxylic acid anilide [4-ethyl-N- (2-oxoperhydro-40)]

Cyclopropanecarboxylic acid -3-furyl) anilide

Untreated control0

Example 9

Limiting concentration test for controlling Pythium ultimum The powdered drug formulations were uniformly mixed with the soil which had been heavily infested with Pythium ultimum. The treated soil was filled into 0.5 liter clay trays and 20 grains of Pisum sativum L. Convar. After cultivation for 3 weeks at 20-24 ° C, the number of healthy peas was determined and the root quality was evaluated (1-4). The active substances, the amounts used and the results are shown in the following table.

Root quality:

= white roots without fungal necroses = white roots, slight fungal necroses = brown roots, already strong fungal necroses = strong fungal necroses, rotten roots

A compound of the invention Concentrate of the active substance in mg / l of soil Number of healthy peas Root quality (1-4) [3-Fluoro-N- (2-oxoper- 20 May 18 4 hydro-3-furyl) anilide] - 40 20 May 4 cyclopropanecarboxylic 80 19 Dec 4 acid [3-bromo-N- (2-oxoper- 20 May 17 4 hydro-3-furyl) anilide] - 40 19 Dec 4 cyclopropanecarboxylates 80 20 May 4 acid [4-fluoro-N- (2-oxoper- 20 May 18 4 hydro-3-furyl) anilide] - 40 19 Dec 4 cyclopropanecarboxylic 80 18 4 acid [2-ethoxy-N- (2-oxoper- 20 May 7 2 hydro-3-furyl) anilide] - 40 17 2 cyclopropanecarboxylic 80 19 Dec 4 acid [3-chloro-N- (5-methyl- 20 May 15 Dec 1 -2-oxoperhydro-3-furyl) - 40 19 Dec 4 anilide j cyclopropanecarboxy- 80 19 Dec 4 acids [3-cyano-N- (2-oxoper- 2Ó 20 May 4 hydro-3-furyl) anilide] - 40 18 4 cyclopropanecarboxylic 80 18 4

acid

A compound of the invention Concentrate of the active substance in mg / l of soil Number of healthy peas Root quality (1-4) [2,3-dichloro-N- (2-oxoper- 20 May - - hydro-3-furyl] anilide acid 40 10 3 cyclopropanecarboxylic 80 11 3 Comparative means ethylene-1,2-bis-dithio- 20 May 3 1 Manganese carbamate 40 8 1 Control 80 10 1 (3 reps) and) 1 1 contaminated soil (b) 0 1 Control II C) 0 1 (3 reps) and) 19 Dec 4 evaporated soil (b) 17 4 C) 18 4

the subject of the invention

Claims (3)

A fungicidal composition, characterized in that it contains as active ingredient at least one cyclopropanecarboxylic acid anilide of the formula I in which: R1 represents a hydrogen atom or a C1 to C4 alkyl group, R @ 2 is an aromatic C @ 6 -carbon radical or once or twice, equally or differently, C1 -C4 -alkyl, C1 -C6 -alkoxy, C1 -C6 -alkylthio, halogen, trifluoromethyl, nitro, C1 -C6 -alkoxycarbonyl, C1 -C4 -alkylcarbonyl and / or cyano-substituted aromatic .alpha.-hydrocarbon radical and n are 1 or 2, optionally in admixture with carriers or excipients. 2. A fungicidal composition as claimed in claim 1, characterized in that it contains at least one of the following compounds of the formula I as active ingredient: [N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [2,6-diethyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [2-methoxy-N- (2- cyclopropanecarboxylic acid oxoperhydro-3-furyl) anilide, [2,6-dimethyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [3-methyl-N- (2-oxoperhydro-3-yl) anilide] ] cyclopropanecarboxylic acid, [4-methyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [2,4-dimethyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [3-chloro Cyclopropanecarboxylic acid N- (2-oxoperhydro-3-furyl) anilide, Cyclopropanecarboxylic acid [3-fluoro-N- (2-oxoperhydro-3-fluoro) anilide], [3-bromo-N- (2- cyclopropanecarboxylic acid oxoperhydro-3-furyl) anilide, [2,6-diisopropyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [2-ethyl-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid, [4-ethyl-N- (2-o cyclopropanecarboxylic acid xoperhydro-3-furyl) anilide, cyclopropanecarboxylic acid [4-fluoro-N- (2-oxoperhydro-3-furyl) anilide], [2-ethoxy-N- (2-oxoperhydro-3-furyl) anilide] cyclopropanecarboxylic acid Cyclopropanecarboxylic acid [3-chloro-2-methyl-N- (2-oxoperhydro-3-furyl) anilide], cyclopropanecarboxylic acid [3-chloro-N- (5-methyl-2-oxoperhydro-3-furyl) anilide], [ Cyclopropanecarboxylic acid 3-ethyl-N- (2-oxoperhydro-3-furyl) anilide, cyclopropanecarboxylic acid [3-cyano-N- (2-oxoperhydro-3-furyl) anilide], [3-thiomethyl-N- (2-oxoperhydro) Cyclopropanecarboxylic acid -3-furyl) anilide, cyclopropanecarboxylic acid [2,3-dichloro-N- (2-oxoperhydro-3-furyl) anilide]. 3. A process for the preparation of the active ingredients of the fungicidal composition according to item 1, i.e. the cyclopropanecarboxylic acid anilides of the general formula I in which: R 1 represents a hydrogen atom or a C 1 -C 4 -alkyl group, R 2 is an aromatic C 1 -C 6 hydrocarbon radical or once or twice, equally or differently C 1 -C 4 -alkyl, C 1 -C 1 -alkoxy, C 1 -C 4 -alkylthio, halogen, trifluoromethyl, nitro, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylcarbonyl and / or a cyano-substituted aromatic C 6 -carbon radical and n are numbers 1 or 2, characterized in that the compounds of the general formula II (CH 2 CH-NH-R _Z) in which: R1, R2 and n are as defined above and react with cyclopropanecarboxylic acid chloride of the formula Cl-CO-CH 1 in the presence of an acid-binding agent and optionally a solvent at a temperature of -10 ° C to + 120 ° C, preferably in equimolar amounts at 0 ° C to room temperature, and the reaction products are isolated.