DE2724785A1 - FURANCARBONIC ANILIDES, FUNGICIDALS CONTAINING THESE COMPOUNDS AND THE PROCESS FOR THEIR PREPARATION - Google Patents

Description

The invention relates to new furancarboxylic acid anilides, fungicidal agents containing these compounds for combating phytopathogenic fungi and processes for the production of the new active ingredients.

Agents that are effective against phytopathogenic fungi are already known. Agents of this type known in the art are, for example, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (US Pat. No. 3,260,725 and 3,260,588) and tetramethylthiuram disulfide (DT-PS 642 532). However, these agents do not always have a satisfactory effect against leaf and soil fungi.

The object of the present invention is to provide an agent with a superior action against leaf and soil fungi.

According to the invention, this object is achieved by an agent which is characterized by a content of at least one compound of the general formula

I,

in which R [deep] 1 is hydrogen or C [deep] 1 -C [deep] 4 -alkyl, R [deep] 2 is an aromatic hydrocarbon radical or one or more, identical or different through C [deep] 1 -C [ deep] 4 -alkyl, C [deep] 1 -C [deep] 4 -alkoxy, C [deep] 1 -C [deep] 4 -alkylthio, halogen, trifluoromethyl, nitro, C [deep] 1 -C [deep] 4 -alkoxycarbonyl, C [deep] 1 -C [deep] 4 -alkylcarbonyl and / or cyano-substituted aromatic hydrocarbon radical and n denotes the numbers 1 or 2.

The compounds according to the invention are surprisingly superior to known agents with the same direction of action in their action against leaf and soil fungi and are also distinguished by good plant tolerance and a sufficient duration of action. Since they also do not have a phytotoxic effect in the application rates which are practically applicable, they can consequently be used advantageously in agriculture and in horticulture to control leaf and soil fungi.

The compounds according to the invention have outstanding fungicidal properties against harmful fungi.

In contrast to the only preventively active fungicidal agents, such as, for example, N-trichloromethylthiophthalimide (US Pat. No. 2,553,770) and Manganäthylenbisdithiocarbamat (US Pat. No. 2,504,404), the compounds according to the invention surprisingly have the additional advantage of being curative and systemic Effect on and therefore also allow the control of pathogens that have already penetrated the plants.

Of the compounds according to the invention, those in particular are distinguished by a superior fungicidal effect in which in the general formula IR [deep] 1 is hydrogen, methyl or ethyl and R [deep] 2 is phenyl, methylphenyl, dimethylphenyl, ethylphenyl, isopropylphenyl, methoxyphenyl, ethoxyphenyl , Methylthiophenyl,

Represent fluorophenyl, chlorophenyl, bromophenyl, dichlorophenyl, trifluoromethylphenyl, nitrophenyl, cyanophenyl, methoxycarbonylphenyl, acetylphenyl or biphenylyl.

The application can take place either with one active ingredient alone or with the mixtures of at least two constitutionally different active ingredients from the series of the claimed compounds. If desired, other fungicides, nematicides, herbicides or other pesticides - depending on the desired purpose - can be added. The active ingredients are expediently in the form of preparations, such as, for example, powders, scattering agents, 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 applied.

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

Lime, kaolin, chalk,

Talc, attaclay and other clays as well as natural or synthetic silica.

Examples of surface-active substances are: salts of lignin sulfonic acid, salts of alkylated benzenesulfonic acids, sulfonated acid amides and their salts, polyethoxylated amines and alcohols.

If the active ingredients are to be used for seed dressing, dyes can also be added in order to give the dressed seed a clearly visible color.

The proportion of the active ingredient (s) in the mean can vary within wide limits, the exact concentration of the active ingredient used for the means mainly depends on the amount in which the means are used, inter alia, for soil or seed treatment or for the treatment of above-ground parts of plants should. For example, the agents contain about 1 to 80 percent by weight, preferably between 20 and 50 percent by weight of active ingredient and about 99 to 20 percent by weight of liquid or solid carriers and optionally up to 20 percent by weight of surface-active substances.

The new compounds of the general formula (I) can be prepared by, for example, compounds of the general formula

II,

in which R [deep] 1, R [deep] 2 and n have the meaning given above, with furancarboxylic acid chloride of the formula reacts in the presence of an acid acceptor and, if appropriate, a solvent, preferably in equimolar proportions, and isolates the process products in a manner known per se.

Acid acceptors that can be used are, for example, organic bases such as pyridine, triethylamine or N, N-dimethylaniline, or inorganic bases such as hydroxides,

Oxides and carbonates of alkali and alkaline earth metals, for example sodium, potassium or calcium.

Ethers, tetrahydrofuran, benzene, ethyl acetate and others, for example, can optionally be used as solvents. Liquid acid acceptors, such as pyridine, can also be used as solvents.

The reaction is expediently carried out at temperatures from -10.degree. C. to 120.degree.

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

example 1

Furan-2-carboxylic acid [N- (2-oxoperhydro-3-furyl) -2,6-dimethylanilide]

206.2 g (1.58 mol) of furan-2-carboxylic acid chloride are added at room temperature to a solution of 300 g (1.46 mol) of 3- (2,6-dimethylanilino) -perhydrofuran-2 in 600 ml of dry pyridine added dropwise. When the addition is complete, the pyridine complex precipitates out with a rise in temperature. The mixture is heated to 50 ° C. for a further 3 hours and then concentrated to half its volume in vacuo. Then it is poured into 2.5 l of ice-cold 5% hydrochloric acid while stirring and, after 30 minutes, sucked. It is washed with plenty of water and dried in vacuo at 70.degree.

Yield: 387 g = 89% of theory

M.p .: 135-138 ° C

Example 2

Furan-2-carboxylic acid [2-chloro-N- (2-oxoperhydro-3-furyl) anilide]

21.16 g (0.1 mol) 3- (2-chloroanilino) -perhydrofuran-2 are mixed with 13.05 g (0.1 mol) furan-2-carboxylic acid chloride at room temperature. The reaction mixture is slowly heated to 120 ° C. and kept at this temperature for 1.5 hours until the evolution of HCl has ended. After cooling, 100 ml of ethyl acetate are added and the mixture is washed neutral with saturated sodium hydrogen carbonate solution. The ethyl acetate phase is dried with magnesium sulfate, filtered and concentrated in vacuo. The remaining oil is crystallized with a little ether, filtered off with suction and the crystals are washed with diisopropyl ether.

Yield: 21.4 g = 70% of theory.

M.p .: 98-100 ° C

Example 3

Furan-2-carboxylic acid [N- (2-oxoperhydro-3-furyl) anilide]

A solution of 14.16 g (0.08 mol) of 3-anilinoperhydrofuran-2 in 150 ml of ethyl acetate and a solution of 9.54 g (0.09 mol) of sodium carbonate in 15 ml of water are mixed with stirring. 11.70 g (0.09 mol) of furan-2-carboxylic acid chloride are then added dropwise while cooling with ice. It is stirred for one hour, neutralized with a little soda solution if necessary and extracted with ethyl acetate. After drying over magnesium sulfate, the ethyl acetate solution is concentrated to dryness in vacuo and the solid residue is treated with a little ether / ethanol. It is filtered off with suction, washed with ether and recrystallized from ethanol.

Yield: 10.6 g = 49% of theory

M.p .: 140-141 ° C

The following compounds according to the invention can also be prepared analogously.

The compounds according to the invention are generally almost colorless, odorless, crystalline bodies that are almost insoluble in water and gasoline, in polar organic

Supplement to the table on page 13

common solvents such as acetone, dimethylformamide and dimethyl sulfoxide, on the other hand, are very soluble.

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

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

Example 4

Limit concentration test in the fight against Pythium ultimum

20% powdery active ingredient preparations were evenly mixed with the soil which was heavily contaminated by Pyhtium ultimum. The treated soil was filled into clay bowls with a capacity of 0.5 liters and, without a waiting period, 20 grain peas of the "Wunder von Kelvedon" variety were sown per bowl. After a cultivation period of 3 weeks at 20 to 24 ° C, the number of healthy peas was determined and a root rating (1-4) was carried out.

Active ingredients, application rates and results are listed in the table below.

Root rating: 4 = white roots without fungal necrosis;

3 = white roots, slight fungal necrosis;

2 = brown roots, already stronger fungal necrosis;

1 = severe fungal necrosis, rotten roots;

Example 5

Dressing of sugar beet seeds

Calibrated sugar beet seeds of the “Dieckmann-Suprapoly” variety were dressed with 20% powdered active ingredient preparations. Clay bowls (20x20x5 cm) containing 2 liters of earth were filled with normal compost soil (daming-off) and 100 grains of sugar beet seeds were sown per bowl. After a culture period of 18 days at 19-21 ° C. in the greenhouse, the healthy seedlings were determined.

Active ingredients, application rates and results are listed in the table below.

Example 6

Control of Pythium splendens in the pot culture of Poinsettia pulcherrima

Rooted young poinsettia plants of the "Annette Hegg Diva" variety were potted in clay pots with a diameter of 11 cm. The potting substrate (peat culture substrate + sandy compost soil 1: 1) was heavily contaminated by Pythium splendens. After potting, the plants were watered once with 100 ml of the specified preparation concentration. This was followed by a cultivation period of 10 weeks at 20 to 21 ° C. in the greenhouse. At the end of the culture, the plant height of 10 plants was measured, the fresh weight of leaves and bracts was determined and a root rating was carried out.

Active ingredients, application rates and results are listed in the table below.

Root rating: 4 = no infestation

3 = low infestation

2 = medium infestation

1 = severe infestation

Example 7

Combating onion soft rot and onion root rot in tulip forcing

Prepared tulip bulbs (5 ° C. tulips) of the "Gander" variety were peeled and 12 bulbs were planted in wooden boxes measuring 27x27x12 cm. The plant substrate (sandy compost) was heavily contaminated by Pythium ultimum and Pythium sylvaticum. The preparation was evenly worked into the potting soil as a 10% powder formulation before planting. This was followed by a cultivation period of 47 days at a soil temperature of 12 to 17 ° C, slowly increasing. The cut flowers were weighed, the loss of plants due to bulb rot was determined and a root scoring was carried out.

Active ingredient, application rates and results are listed in the table below.

Root rating: 4 = no infestation

3 = low infestation

2 = medium infestation

1 = severe infestation

Example 8

Control of Phytophthora parasitica var. Nicotianae in the pot culture of Sinningia speciosa (gloxinia)

Sinningia young plants of the "Gierth`s Blaue" variety were potted in clay pots with a diameter of 11 cm. The pot substrate was a mixture of peat culture substrate and sandy compost soil 1: 1. After potting, the plants were watered once with 100 ml of the specified preparation concentration. 3 days later, the pots were uniformly inoculated with mycelium flakes from a three-week-old phytophthora culture. This was followed by a culture period of 7 weeks at 22 to 24 ° C in the greenhouse.

Active ingredient, application rates and results are listed in the table below.

Example 9

Control of Pythium ultimum in the propagation of pelargonium cuttings

Clay pots with a diameter of 6 cm were filled with the propagation substrate, which was heavily contaminated by Pythium ultimum. The substrate was a mixture of 3 parts of peat culture substrate and 2 parts of sand. 30 ml of the stated active compound concentration were then poured onto the soil surface in each pot. Thereafter, unrooted shoot tips of Pelargonium peltatum, variety "Luisenhof", were placed in 24 pots per test series. After a culture period of 25 days at 22 to 25 ° C in the propagation bed, the loss of plants was determined, the average fresh weight of the rooted cuttings was determined.

Active ingredients, application rates and results are listed in the table below.

Example 10

Effect of prophylactic foliar treatment against Plasmopara viticola on grapevine plants in the greenhouse

Young grapevine plants with about 5 to 8 leaves were sprayed to runoff at the specified concentration, after the spray coating had dried on with an aqueous suspension of sporangia of the fungus (about 20,000 per ml), and immediately in the greenhouse at 22 to 24 ° C and an atmosphere saturated with water vapor incubated. From the second day on, the humidity was reduced to normal for 3 to 4 days (30 to 70% saturation) and then kept at water vapor saturation for a further day. The percentage of the area infected with fungi was then noted for each leaf, and the average per treatment to determine the fungicidal effect was calculated as follows:

*) Effect is based on 100% infestation in the untreated control.

Example 11

Effect of prophylactic leaf treatment against Phytophthora infestans on tomato plants or on potato plants in the greenhouse

Young tomato plants with at least 2 developed leaves or potato plants (for example from eye cuttings) of at least 10 cm in height were sprayed to runoff at the specified concentration and, after the spray coating had dried on, with an aqueous, 50,000 to 80,000 sporangia of the fungus in milliliters and about 2 Sprayed suspension incubated for hours in a refrigerator at 11 ° C. The plants were incubated at high atmospheric humidity and about 15 to 18 ° C. in the greenhouse and the percentage of infected leaf area was assessed after about 5 days. The fungicidal effect was calculated as follows:

*) Effect is based on 100% infestation in the untreated control

Example 12

Systemic effect of a soil treatment against Phytophthora infestans on tomato plants or on potato plants in the greenhouse

The weighed substances (weight per volume) were mixed in soil, the soil was filled into plant pots and young tomato plants with at least 2 developed leaves or potato plants (for example from cuttings) with a height of at least 10 cm were used. After the desired set time had elapsed (for example after 3 days), the plants were sprayed with an aqueous suspension containing 50,000 to 80,000 sporangia of the fungus in the milliliter and incubated for about 2 hours in a refrigerator at 11 ° C. The plants were incubated at high atmospheric humidity and about 15 to 18 ° C. in the greenhouse and the percentage of infected leaf area was assessed after about 5 days. The fungicidal effect was calculated as follows:

Systemic effect of soil treatment against Phytophthora infestans on tomato plants (weight of active ingredient / volume)

* Effect is based on 100% infestation in the untreated control.

Example 13

Curative effect of a foliar treatment against Phytophthora infestans on tomato plants or on potato plants in the greenhouse

Young tomato plants with at least 2 developed leaves or potato plants (for example from eye cuttings) at least 10 cm high were sprayed with an aqueous suspension containing 50,000 to 80,000 milliliters of sporangia of the fungus and incubated for about 2 hours in a refrigerator at 11 ° C. The plants were incubated at high humidity. After the desired specified time had elapsed, the plants were sprayed to runoff with the concentration of the fungicide to be tested within the period of latent fungal attack. After the outbreak of fungal attack in the untreated control plants, the percentage of infected leaf area was assessed. The fungicidal effect was calculated as follows:

* Effect is based on 100% infestation in untreated controls.

Claims (49)

1. Furancarboxylic acid anilides of the general formula I, in which R [deep] 1 is hydrogen or C [deep] 1 -C [deep] 4 -alkyl, R [deep] 2 is an aromatic hydrocarbon radical or one or more, identical or different through C [deep] 1 -C [ deep] 4 -alkyl, C [deep] 1 -C [deep] 4 -alkoxy, C [deep] 1 -C [deep] 4 -alkylthio, halogen, trifluoromethyl, nitro, C [deep] 1 -C [deep] 4 -alkoxycarbonyl, C [deep] 1 -C [deep] 4 -alkylcarbonyl and / or cyano-substituted aromatic hydrocarbon radical and n denotes the numbers 1 or 2. 2. Furan-2-carboxylic acid [N- (2-oxoperhydro-3-furyl) -2,6-dimethylanilide]. 3. Furan-2-carboxylic acid [2-chloro-N- (2-oxoperhydro-3-furyl) anilide]. 4. Furan-2-carboxylic acid [N- (2-oxoperhydro-3-furyl) anilide]. 5. Furan-2-carboxylic acid [2,6-diethyl-N- (2-oxoperhydro-3-furyl) anilide]. 6. Furan-2-carboxylic acid [2-ethyl-6-methyl-N- (2-oxoperhydro-3-furyl) anilide]. 7. Furan-2-carboxylic acid [2-methoxy-N- (2-oxoperhydro-3-furyl) anilide]. 8. Furan-2-carboxylic acid [2,6-dimethyl-N- (5-methyl-2-oxoperhydro-3-furyl) anilide]. 9. Furan-2-carboxylic acid [3,4-dichloro-N- (2-oxoperhydro-3-furyl) anilide]. 10. Furan-2-carboxylic acid [2-methyl-N- (2-oxoperhydro-3-furyl) anilide]. 11. Furan-2-carboxylic acid [2,4-dimethyl-N- (2-oxoperhydro-3-furyl) anilide]. 12. Furan-2-carboxylic acid [3,4-dimethyl-N- (2-oxoperhydro-3-furyl) anilide]. 13. Furan-2-carboxylic acid [2,3-dimethyl-N- (2-oxoperhydro-3-furyl) anilide]. 14. Furan-2-carboxylic acid [3,5-dimethyl-N- (2-oxoperhydro-3-furyl) anilide]. 15. Furan-2-carboxylic acid [2,4,6-trimethyl-N- (2-oxoperhydro-3-furyl) anilide]. 16. Furan-2-carboxylic acid [3-methyl-N- (2-oxoperhydro-3-furyl) anilide]. 17. Furan-2-carboxylic acid [4-methyl-N- (2-oxoperhydro-3-furyl) anilide]. 18. Furan-2-carboxylic acid [3-chloro-N- (2-oxoperhydro-3-furyl) anilide]. 19. Furan-2-carboxylic acid [4-chloro-N- (2-oxoperhydro-3-furyl) anilide]. 20. Furan-2-carboxylic acid [2-ethyl-N- (2-oxoperhydro-3-furyl) anilide]. 21. Furan-2-carboxylic acid [N- (2-oxoperhydro-3-furyl) -3-trifluoromethylanilide]. 22. Furan-2-carboxylic acid [4-isopropyl-N- (2-oxoperhydro-3-furyl) anilide]. 23. Furan-2-carboxylic acid [3-bromo-N- (2-oxoperhydro-3-furyl) anilide]. 24. Furan-2-carboxylic acid [4-methoxy-N- (2-oxoperhydro-3-furyl) anilide]. 25. Furan-2-carboxylic acid [4-ethoxy-N- (2-oxoperhydro-3-furyl) anilide]. 26. Furan-2-carboxylic acid [4-ethyl-N- (2-oxoperhydro-3-furyl) anilide]. 27. Furan-2-carboxylic acid [4-bromo-N- (2-oxoperhydro-3-furyl) anilide]. 28. Furan-2-carboxylic acid [3-fluoro-N- (2-oxoperhydro-3-furyl) anilide]. 29. Furan-2-carboxylic acid [4-fluoro-N- (2-oxoperhydro-3-furyl) anilide]. 30. Furan-2-carboxylic acid [4-methoxy-2-methyl-N- (2-oxoperhydro-3-furyl) anilide]. 31. Furan-2-carboxylic acid [2,5-dimethyl-N- (2-oxoperhydro-3-furyl) anilide]. 32. Furan-2-carboxylic acid [2-ethoxy-N- (2-oxoperhydro-3-furyl) anilide]. 33. Furan-2-carboxylic acid [2,6-diisopropyl-N- (2-oxoperhydro-3-furyl) anilide]. 34. Furan-2-carboxylic acid [3,5-dichloro-N- (2-oxoperhydro-3-furyl) anilide]. 35. Furan-2-carboxylic acid [3-chloro-2-methyl-N- (2-oxoperhydro-3-furyl) anilide]. 36. Furan-2-carboxylic acid [5-chloro-2-methyl-N- (2-oxoperhydro-3-furyl) anilide]. 37. Furan-2-carboxylic acid [2-methoxycarbonyl-N- (2-oxoperhydro-3-furyl) anilide]. 38. Furan-2-carboxylic acid [3-methoxy-N- (2-oxoperhydro-3-furyl) anilide]. 39. Furan-2-carboxylic acid [3-nitro-N- (2-oxoperhydro-3-furyl) anilide]. 40. Furan-2-carboxylic acid [3-chloro-N- (5-methyl-2-oxoperhydro-3-furyl) anilide]. 41. Furan-2-carboxylic acid [3-methylthio-N- (2-oxoperhydro-3-furyl) anilide]. 42. Furan-2-carboxylic acid [5-chloro-2-methoxy-N- (2-oxoperhydro-3-furyl) anilide]. 43. Furan-2-carboxylic acid [3-fluoro-N- (5-methyl-2-oxoperhydro-3-furyl) anilide]. 44. Furan-2-carboxylic acid [4-phenyl-N- (2-oxoperhydro-3-furyl) anilide]. 45. Furan-2-carboxylic acid [3-acetyl-N- (2-oxoperhydro-3-furyl) anilide]. 46. Process for the preparation of furancarboxylic acid anilides of the general formula I, in which R [deep] 1 is hydrogen or C [deep] 1 -C [deep] 4 -alkyl, R [deep] 2 is an aromatic hydrocarbon radical or one or more, identical or different through C [deep] 1 -C [ deep] 4 -alkyl, C [deep] 1 -C [deep] 4 -alkoxy, C [deep] 1 -C [deep] 4 -alkylthio, halogen, trifluoromethyl, nitro, C [deep] 1 -C [deep] 4 -alkoxycarbonyl, C [deep] 1 -C [deep] 4 -alkylcarbonyl and / or cyano-substituted aromatic hydrocarbon radical and n denotes the numbers 1 or 2, characterized in that compounds of the general formula II, in which R [deep] 1, R [deep] 2 and n have the meaning given above, with furancarboxylic acid chloride of the formula reacts in the presence of an acid acceptor and, if appropriate, a solvent, preferably in equimolar proportions, and isolates the process products in a manner known per se. 47. Fungicidal agents, characterized by a content of at least one compound according to Claims 1 to 45. 48. Fungicidal agents, characterized by a content of at least one compound produced by the method according to claim 46. 49. Fungicidal agents according to claims 47 or 48 in a mixture with carriers or auxiliaries.