NO149431B - FURANCARBOXYLIC ACID ANILIDES WITH FUNGICIDE EFFECT - Google Patents

Description

The present invention relates to new furancarboxylic acid anilides with fungicidal action for combating phytopathogenic fungi.

Agents with activity against phytopathogenic fungi are previously known. Means of this kind known in practice are e.g. 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (U.S. Patent 3,260,725 and 3,260,588) and tetramethylthiuram disulfide (DE Patent 642,532). However, these agents do not always show a satisfactory effect against leaf and soil fungi.

The task for the present invention is to provide an agent with superior action against leaf and soil fungi. The furancarboxylic acid anilides according to the invention appear in claim 1

The compounds according to the invention are surprisingly superior to agents with the same type of action in their action against leaf and soil fungi, and are also distinguished by good plant compatibility and a sufficient duration of action. As they also do not have a phytotoxic effect at the quantities used in practice, they can therefore be used with advantage in agriculture and in gardens to combat leaf and soil fungi.

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

In contrast to the known fungicidal agents that only act prophylactically, such as e.g. N-t riclormethylthiophthalimide (U.S. Pat.

2,553,770) and manganese ethylene bisdithiocarbamate (U.S. Pat

2 50'4 kOk) t surprisingly, the compounds according to the invention exhibit the further advantage of a curative and systemic effect and therefore also allow the combating of pathogens that have already penetrated the plants.

Of the compounds according to the invention, furan-2-carboxylic acid-[2,6-dimethyl-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide], furan-2-carboxylic acid-[3-fluoro-N -(2-oxoperhydro-3-furyl)-anilide and furan-2-carboxylic acid-[3-chloro-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide] by a superior fungicidal action, as it appears

of the trial report.

The application can take place either with an active substance alone or also with mixtures of at least two constitutionally different active substances from the range of present compounds. Optionally, other fungicides, nematicides, herbicides or other pest control agents can be added, depending on the desired purpose. Appropriately, the active substances are used in the form of preparations such as e.g. powders, flow agents, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers, respectively fertilizers and possibly wetting, binding, emulsifying and/or dispersing aids.

Suitable liquid carriers are water, mineral oil or other organic solvents, such as e.g. xylene, chlorobenzene, cyclohexanol, cyclohexanone, dioxane, acetonitrile, acetic acid ester, dimethylformamide, isophorone and dimethylsulfoxyd.

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

Surface-active substances can e.g. are mentioned: salts of ligninsulfonic acid, salts of alkylated benzenesulfonic acids, sulfonated acid amides and their salts, polyethoxylated amines and alcohols.

When the active substances are to be used for seed staining, dyes can also be mixed to give the stained seed material a clearly visible colour.

The amount of it, respectively the active substances in the remedy can vary within wide limits, as the exact concentration of the active substance used for the remedy mainly depends on the quantity in which the remedy, among other things, a. must be used for soil or seed treatment or for the treatment of above-ground plant parts. For example, midLet contains approx. 1 to 80% by weight, preferably between 20 and 50% by weight active substance and approx. 99 to 20% by weight of liquid or solid surfactants as well as possibly up to 20% by weight of surfactants.

The new compounds with the general formula I can be prepared by e.g. reacts compounds with the general formula:

where R^ and R~ are as stated above, with furancarboxylic acid chloride with the formula: in the presence of an acid acceptor and possibly a solvent, preferably in equimolar amounts, and isolates the process product in a manner known per se .

As acid acceptors can be used e.g. organic bases such as pyridine, triethylamine or N,N-dimethylaniline, or inorganic bases such as hydroxides, oxides and carbonates of alkali and alkali metal, such as e.g. sodium, potassium or calcium.

As a solvent, e.g. ether,

tetrahydrofuran, benzene, acetic acid ester and others. Liquid acid acceptors such as pyridine, can also be used as a solvent.

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

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

Example or 1

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

To a solution of 300 g (1.46 mol) 3~(2,6-dimethylanilino)-perhydrofuranone-2 in 600 ml dry pyridine, 206.2 g (1.58 mol) furan-2 is added dropwise at room temperature with stirring -carboxylic acid chloride. After completion of the addition, the pyridine complex precipitates during a rise in temperature. It is heated for a further 3 hours at 50°C and then evaporated in vacuum to half the volume. The reaction mixture is then poured with stirring into 2.5 l of ice-cold 5% hydrochloric acid and filtered off with suction after 30 minutes. Wash with plenty of water and dry in a vacuum at 70°C.

Yield: 387 g ■<=> 89% of the theoretical.

Melting point: 135 - 138°C.

Example 2

Furan-2-carboxyl urea-[2-chloro-N-(2-oxoperhydro-3-furyl)-anilide]

21.16 g (0.1 mol) of 3-(2-chloroanilino)-perhydrofuranone-2 are added at room temperature to 13.05 g (0.1 mol) of furan-2-carboxylic acid chloride. The reaction mixture is slowly heated to 120°C and kept at this temperature for 1.5 hours until hydrogen chloride evolution has stopped. After cooling, 100 ml of acetic acid ester is added, and there it is washed neutrally with saturated sodium hydrogen carbonate solution. The acetic acid ester phase is dried with magnesium sulfate, filtered and evaporated in a vacuum. 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 the theoretical.

Melting point: 98 - 100°C.

Example 3

Furan-2 -ca rboxy 1 sy r.e-j N - (2 -oxo per hy d ro - 3- f uryl) -an iljd]

A solution of 14.16 g (0.08 mol) of 3-a nilinoperhydro - furanone-2 in 150 ml of acetic acid ester and a solution of 9.54 9

(0.09 mol) nat r lumcarbonate in 15 nil water is mixed with stirring. 11.70 g (0.09 mol) of furan-2-carboxylic acid chloride are then added dropwise

under ice cooling. It is stirred for a further 1 hour, neutralized with a little soda solution if necessary and clarified with acetic acid ester. After drying over magnesium sulfate, the acetic acid ester solution is evaporated to dryness in a vacuum, and the solid residue is treated with a little ether/ethanol. The mixture is again filtered off with suction, washed with ether and recrystallized from ethanol.

Yield: 10.6 g 49% of the theoretical.

Melting point: 140 - 141°C.

Analogously, the following compounds according to the invention can also be prepared.

The compounds according to the invention are, as a rule, almost colorless, odorless, crystalline substances which are almost insoluble in water and petrol, but which, on the other hand, are very soluble in polar organic solvents such as e.g. acetone, dimethylformamide and dimethylsulfoxide.

The starting compounds for the production of the compounds according to the invention are known in and of themselves or can be produced by methods known in and of themselves.

The following examples serve to illustrate the possibility of use for the compounds according to the invention.

Attempt 1

Limit concentration test for control of Pythium ultimum

20% powdered active ingredient preparations were mixed evenly with the soil, which was heavily infected with Pythium ultimum. The treated soil was filled in clay bowls that took 0.5 1 of soil and 20 marked grains of the variety "Wunder von Kelvedon" were sown in each bowl without a withdrawal period. After a cultivation period of 3 weeks at 20 - 24°C, the number of healthy peas was determined, and a root assessment (1 - 4) was carried out.

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

Attempt 2

Be icing sugar beet seeds

Calibrated sugar beet seeds of the species "Dieckmann-Suprapoly" were stained with 20% powdered active ingredient preparations. Clay bowls that took 2 1 of soil (20 x 20 x 5 cm) were filled with normal compost soil ("Daming-off"), and in each bowl 100 sugar beet seeds were sown. After a cultivation period of 18 days at 19 - 21 C in a greenhouse, the healthy seedlings were determined.

The active substance, application amount and result are indicated in the table below.

Attempt 3

Control of Pythium splendens by pot cultivation of Poinsettia pulcherrima

Poinsettia seedlings of the variety "Annette Hegg Diva" with roots were planted in clay pots with a diameter of 11 cm. The potting substrate (pot culture substrate + sandy compost soil 1:1) was heavily infected with Pythium splendens. After planting in pots, the plants were overwashed once with 100 ml of the specified preparation concentration. The cultivation period lasted 10 weeks at 20 - 21°C in a greenhouse. The plant height of each of the 10 plants was measured at the end of cultivation, the fresh weight of leaves and bracts of the plants was determined, and a root assessment was carried out.

Active substances, application amounts and results are indicated in the following table.

Attempt 4

Control of onion soft rot and onion root rot in tulip cultivation

Prepared tulip bulbs (5°C tulips) of the variety "Gander" were peeled, and 12 bulbs were planted in each wooden box of size 27 x 27 x 12 cm. The plant substrate (sandy compost soil) was heavily infected with Pythium ultimum and Pythium sylvaticum. In the planting soil, the preparation as a 10% powdered preparation was incorporated evenly before planting. The bulbs were then grown for 47 days at a slowly rising soil temperature of 12 to 17°C. The ready-to-cut flowers were weighed, the plant loss due to bulb rot was determined, and a root assessment was carried out.

Active substance, application amounts and results are indicated in the following table.

Attempt 5

Control of Phytophthora parasitica var. nicotianae in pot culture of Sinningia speciosa (Gloxinie)

Sinningia saplings of the variety "Gierth's Blaue" were planted in clay pots with a diameter of 11 cm. The potting substrate was a mixture of peat culture substrate and sandy compost soil 1:1. After planting, the plants were overwashed once with 100 ml of the stated preparation concentration. 3 days later, the pots were inoculated evenly with mycelial fluff of a 3-week-old Phytophthora culture. This was followed by cultivation for 7 weeks at 22 to 24°C in a greenhouse.

Active substance, application amounts and results are indicated in the following table.

Attempt_6

Control of Pythium ultimum in cuttings propagation of pelargonium

Clay pots with a diameter of 6 cm were filled with the propagation substrate that was heavily infected with Pythium ultimum. The substrate was a mixture of 3 parts peat culture substrate and 2 parts sand. Each pot was then covered with the specified concentration of active substance on the soil surface. Then, rootless cuttings of Pelargonium peltatum, variety "Luisenhof", were planted in 24 pots in each trial series. After a cultivation period of 25 days at 22 - 25°C in propagation beds, the plant loss was determined, and the average fresh weight of the cuttings with root was determined.

Active substances, application rates and results are indicated in the following table.

Attempt 7

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

Young vine plants with approx. 5 to 8 leaves were sprayed dripping wet with the indicated concentration, and after drying off. the spray coating, the underside of the leaves was sprayed with an aqueous slurry of spore capsules of the fungus (approx. 20,000 per ml), and immediately incubated in a greenhouse at 22 - 24°C and as much water vapor-saturated atmosphere as possible. From the second day, the humidity for the 3rd to 4th day was brought back to normal (30 - 70% saturation) and then for a further day held at water vapor saturation. Then, for each leaf, the percentage of the surface infested by the fungus was noted, and the average of each treatment was recalculated to find the fungicidal effect as follows:

Attempt 8

The effect of prophylactic foliar treatment against Phytophthora infestans on tomato plants or potato plants in greenhouses

Young tomato plants with at least two developed leaves or potato plants (e.g. from eye cuttings) at least 10 cm high were sprayed dripping wet with the indicated concentration and, after drying the spray coating, were sprayed with an aqueous suspension containing 50,000 to 80,000 spore capsules of the fungus per ml and incubated for 2 hours in a refrigerator at 11°C. The plants were incubated at high humidity and approx. 15 - 18°C in a greenhouse, and after approx. After 5 days, the percentage of the infested leaf area was assessed. The fungicidal effect is calculated as follows:

Attempt 9

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

Field soil was mixed with the weighed substances (weight per volume), the soil was filled in plant pots, and young tomato plants with at least 2 developed leaves or potato plants (e.g. from eye cuttings) of at least 10 cm height were planted there. After the expiry of the desired pre-application time (e.g. after 3 days), the plants were sprayed with an aqueous suspension containing 50,000 to 80,000 spore capsules of the fungus per ml and which was incubated for approx.

2 hours in a refrigerator at 11°C. The plants were incubated at high humidity and approx. 15 to 18°C in a greenhouse, and after approx. After 5 days, the percentage of the infested leaf surface was assessed. The fungicidal effect was calculated as follows:

■ Attempt 10

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

Young tomato plants with at least 2 developed leaves or tomato plants (e.g. from eye cuttings) of at least 10 cm height were sprayed with an aqueous suspension containing 50,000 to 80,000 spore capsules of the fungus per ml and which was incubated for approx. 2 hours in a refrigerator at 11°C. The plants were incubated at high humidity. After the expiry of the desired pre-application time, within the time of latent fungal attack, the plants were sprayed with the concentration of the fungicide to be tested while still wet. After the outbreak of the fungal attack on the untreated control plants, the percentage of the attacked leaf surface was assessed. The fungicidal effect was calculated as follows:

Attempt 11

Young tomato plants were sprayed dripping wet with those i

active substance concentrations indicated in the table. After drying of the spray coating, the treated plants as well as untreated ones were inoculated by spraying a suspension of spores (about 1 million per ml of fruit juice solution) of the gray mold producer Botrytis cinerea and incubated moist at about 20°C in a greenhouse. After the collapse of the untreated plants (= 100% damage), the degree of damage of the treated plants was determined and the fungicidal effect calculated as follows:

In addition, plant compatibility was determined by assessment, with damage above 10% being judged as intolerable and damage below 10% as tolerable.

The following compounds were tested as active ingredients from the present patent application: Furan-2-carboxylic acid-[2,6-dimethyl-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide], Furan-2-carboxylic acid-[3 -fluoro-N-(2-oxoperhydro-3-furyl)-anilide], Furan-2-carboxylic acid-[3-chloro-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide.

As comparison compounds were tried

3-(N-propionyl-N-4-chlorophenylamino)-γ-butyllactone

(US patent 3,933,860)

N-(1'-methoxycarbonyl-ethyl)-N-(furan-(2"-carbonyl)-2,6-dimethyl-aniline

(Norwegian patent 141 340)

The results were indicated in the following table

Claims (4)

1. Furancarboxylic acid anilides with fungicidal action, characterized in that they have the general formula: where R 1 is hydrogen or alkyl with 1-4 carbon atoms, phenyl which is optionally substituted with one or more of the substituents is alkyl with 1-4 carbon atoms and/or halogen. 2. Compound according to claim 1, characterized in that it is furan-2-carboxylic acid-[2,6-dimethyl-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide]. 3. Compound according to claim 1, characterized in that it is furan-2-carboxylic acid-[3-fluoro-N-(2-oxoperhydro-3-furyl)-anilide]. 4. Compound according to claim 1, characterized in that it is furan-2-carboxylic acid-[3-chloro-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide].