Succinimide compound

Abstract

Compound of formula (1):

Description

Field of the InventionThe present invention relates to a succinimide compound of the following formula (1): and its use for controlling Pythium spp.Prior ArtA succinimide compound of the following formula: is a known herbicide (flumioxazin), and is described, for example, by Daughrois et al.Non-patent literature: Daughrois, J.H.; Hoy, J.W.; Griffin, J.L.: Protoporphyrinogen oxidase inhibitor herbicide effects on pythium root red of sugarcane, Pythium species, and the soil microbial communication, Phytopathology, Vol. 95, 2005, No. 3, pp. 220-226.Summary of the InventionThe present invention provides the novel succinimide compound of the above formula (1) having a Pythium spp. controlling activity.The compound of formula (1) [compound (1)] is a compound having activity against Pythium spp., for example, Pythium zingiberis and Pythium debaryanum, and can be used as an active ingredient of pythium controlling agents.DETAILED DESCRIPTIONThe process for producing compound (1) will be described below. Compound (1) can be prepared by reacting a compound of formula (2): with a compound of formula (3): .The amount of the compound of the formula (3) [compound (3)] is not particularly limited in this reaction, and is preferably 0.9 to 2 equivalents, and more preferably 1.0 to 1.2 equivalents, based on one equivalent of the compound of the formula (2) [compound (2)].The reaction can be carried out in a suitable solvent. The solvent is not particularly limited as long as it does not result in byproducts by reacting with a reaction substrate, a reactant, and a product. However, solvents are expedient which sufficiently dissolve both the reaction substrate and the reaction partner. Examples of solvents are aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; acid amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and carbon tetrachloride; fatty acids such as formic acid and acetic acid; and mixtures of these solvents.The reaction temperature is usually about 50 to 200°C, and preferably about 80 to 150°C. The reaction time is generally about 0.1 to 48 hours, and preferably 1 to 24 hours.After completion of the reaction, the reaction mixture is subjected to usual post-treatments such as concentration under reduced pressure, solvent extraction, crystallization, recrystallization and chromatography, and thus the compound of the present invention can be isolated and purified.Compound (2) can be prepared as described in JP-A-61-140573. Compound (3) is a commercially available compound. The cis-form of compound (3), namely cis-cyclohex-4-enedicarboxylic anhydride, can also be prepared by a Diels-Alder reaction of maleic anhydride and butadiene.Compound (1) can be applied as it is to a site where pythium increases, thereby exhibiting a controlling effect. Usually, however, it is used in the form of a composition comprising compound (1) and a carrier. The composition is usually prepared in the form of formulations such as emulsion concentrates, wettable powders, water-dispersible granules, suspension concentrates (flowables), dusts or granules by mixing compound (1), a solid carrier and / or a liquid carrier and adding a surfactant and other formulation aids as required. In these formulations, compound (1) is usually contained in an amount of 0.1 to 90% by weight.Examples of the solid carrier used for the formulation are fine powders or granules of minerals such as kaolin clay, attapulgite clay, bentonite, montmorillonite, acid clay, pyrophyllite, talc, diatomaceous earth and calcite, natural organics such as corncob powder and walnut shell powder, synthetic organics such as urea, salts such as calcium carbonate and ammonium sulfate, and synthetic inorganics such as synthetic hydrous silica. Examples of the liquid carrier are aromatic hydrocarbons such as xylene, alkylbenzene and methylnaphthalene, alcohols such as 2-propanol, ethylene glycol, propylene glycol and ethylene glycol monoethyl ether, ketones such as acetone, cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, aliphatic petroleum hydrocarbons, esters, dimethyl sulfoxide, acetonitrile and water.Examples of the surfactant include anionic surfactants such as salts of alkylsulfuric acid esters, alkylarylsulfonic acid salts, dialkylsulfosuccinic acid salts, salts of polyoxyethylene alkylaryl ether phosphoric acid esters, ligninsulfonic acid salts, and formaldehyde-polycondensed naphthalenesulfonate, and nonionic surfactants such as polyoxyethylene alkylaryl ethers, polyoxyethylene alkylpolyoxypropylene block copolymers, and sorbitan fatty acid esters.Examples of other formulation aids are water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone, gum arabic, alginic acid and salts thereof, polysaccharides such as CMC (carboxymethylcellulose) and xanthan gum, inorganics such as aluminum magnesium silicate and alumina sol, preservatives, colorants and PAP (acidic isopropyl phosphate), and stabilizers such as BHT.Pythiumis a genus of Oomycetes, and in this genus, there are also species leading to infectious soil diseases which damage crop plants. They are found in soils from unmanned land and river pools or the like. Sites where the Pythium spp. to be controlled proliferate may be soils from crop land and water sources, as well as plant tissue from crop plants, flowers and the like. The plants used as the host by Pythium spp. may be various plants grown as crop plants, and it is known, for example, that Pythium zingiberisplants such as Gingwer and Japanese Gingwer and Pythium debaryanumplants such as cucumbers, peas, bottle crabgrass and dahlias are used as the host.The composition of the present invention is applied to a plant body used by Pythium spp. as a host. Pythium spp. can be controlled in this way because the plant can be protected from pythium diseases. Further, the composition is applied to the soil or the like in which the plant is grown, and thus Pythium spp. can be controlled in the soil because the plant grown in the soil can be protected from Pythium diseases.When the composition is applied to the foliage of a plant body, or when the composition is applied to soils, the amount applied may vary with the type of crop to be controlled, the type of disease to be controlled, the degree of infestation with the disease to be controlled, the type of formulation, the time of application, weather conditions and the like. Usually, the amount is 1 to 5,000 g, and preferably 5 to 1,000 g, of compound (1) per 10,000 m of 2. Emulsion concentrates, wettable powders, suspension concentrates and the like are usually applied by diluting and spraying them with water. In this case, the concentration of the compound of the present invention is usually in the range of 0.0001 and 3 wt%, and preferably 0.0005 and 1 wt%. Dusts, granules and the like are usually applied unchanged without dilution.When the composition of the present invention is applied to a plant body, it can be applied to the seed, and thus the plant can be protected from pythium diseases. Examples of such methods are methods for impregnating the seeds of a plant in the composition of the invention with a concentration of compound (1) of 1 to 1,000 ppm, methods for spraying or coating the plant with the composition of the invention with a concentration of compound (1) of 1 to 1,000 ppm, and methods for coating the seeds with dust of the composition of the invention.The method of controlling Pythium spp. according to the invention is usually carried out by applying an effective amount of the composition according to the invention to a plant in which Pythium diseases are expected or to soils in which the plant grows. The composition of the present invention is usually used as an agricultural and horticultural fungicide, for example, for controlling pythium diseases on cereal fields, pasture areas, turf fields, tea fields, rice fields, in fruit gardens and the like.The composition of the invention may also be used together with other fungicides, insecticides, acaricides, nematicides, herbicides, plant growth regulators and / or fertilizers.ExamplesThe present invention will be described below in detail by way of Examples.In the examples, elution in column chromatography was followed by TLC (thin layer chromatography). Silica gel 60F254(70-230 mesh; Merck & Co., Inc.) was used for the TLC plate in the following by TLC; the solvent used as eluent in column chromatography was used as the eluent; and a UV detector was used for detection.Silica gel 60 (70 to 230 mesh; Merck & Co., Inc.) was also used as silica gel for the column. When a mixed solvent is used as the developing agent, numerical values in parentheses indicate the volumetric mixing ratio of the solvents.The NMR spectra show proton NMR determined with a JEOL AVANCE 400 (400 MHz) spectrometer using tetramethylsilane as an internal standard. All delta values are given in ppm. The measurement temperature is 25° C. The abbreviations used in the following preparation example have the following meanings:s: singlet, brs: broad singlet, d: doublet, t: triplet,q: quartet, m: multiplet.Room temperature is also about 15 to 25°C.An example of the preparation of the compound of the present invention will be described below.Production Example 1Synthesis of the compound of the invention N-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1,4-benzoxazin-6-yl]cyclohex-4-ene-1,2-dicarboxamid Cyclohex-4-enedicarboxylic anhydride (24.05 g) and 6-amino-7-fluoro-4-(2-propynyl)-2H-1,4-benzoxazin-3-(4H)-one (29.01 g) were dissolved in 132 ml of acetic acid and heated under reflux for 6 1 / 2 hours. The reaction mixture was added to 400 ml of water, and the precipitated crystals were filtered off. The resulting crystals were recrystallized from ethyl acetate to obtain N-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1,4-benzoxazin-6-yl]cyclohex-4-ene-1,2-dicarboxamid (14.31 g).Melting point: 192 to 194°C1 H-NMR (CDCl 3): 2,29 (1 H, t, J=2.4 Hz), 2.32-2.37 (2H, m), 2.71 (2H, d, J=15.6 Hz), 3.32 (2H, s), 4.66 (2H, d, J=2.4 Hz), 4.67 (2H, s), 6.01 (2H, t, J=2.8 Hz), 6.89 (1H, d, J=9.6 Hz), 7.00 (1H, br)Formulation examples are shown below. Here, parts are by weight.Formulation Example 150 Parts of compound (1), 3 parts of calcium lignin sulfonate, 2 parts of magnesium lauryl sulfate and 45 parts of synthetic hydrous silica were well ground and mixed into a wettable powder.Formulation Example 220 Parts of compound (1) and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and the mixture was finely ground by a wet grinding method. Subsequently, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate was added, 10 parts of propylene glycol was further added, and the resultant product was stirred and mixed to give a suspension concentrate.Formulation Example 32 Parts of compound (1), 88 parts of kaolin clay and 10 parts of talc were finely ground and mixed into a dust.Formulation Example 45 Parts of Compound (1), 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene were well mixed to an emulsion concentrate.Formulation Example 52 Parts of Compound (1), 1 part of synthetic hydrous silica, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of kaolin clay were well ground and mixed, then water was added thereto, and the resulting mixture was well kneaded, granulated and dried to obtain granules.Formulation Example 60,1 Parts of compound (1) and 99.9 parts of dimethyl sulfoxide were mixed to obtain a solution.Test Example 1: Antibacterial Test on Pythium zingiberisA predetermined amount of compound (1) was dissolved in dimethyl sulfoxide, and the resulting solution was added to a potato extract-dextrose agar (PDA) medium to a final concentration of 500 ppm.Independently, a bacterial-containing agar piece cut out from the peripheral part of bacterial flora of Pythium zingiberisis precultured in a PDA medium free of additives was inoculated on the PDA medium containing compound (1) and cultured at 12°C or 27°C. Then, the inhibition of mycelium growth was determined according to the following formula 1:The results are shown in Table 1. Table 1 Table 127° CDay 15312° CDay 4100Test Example 2: Antibacterial Test on Pythium zingiberisisA predetermined amount of compound (1) was dissolved in dimethyl sulfoxide, and the resulting solution was added to a potato extract-dextrose agar (PDA) medium to a final concentration of 500 ppm.Independently, a bacterial-containing agar piece cut out from the peripheral portion of the bacterial flora of Pythium zingiberisis precultured in a PDA medium free of additives was inoculated on the PDA medium containing compound (1) and cultured at 27°C for 4 days. Then, the inhibition of mycelium growth was determined by Formula 1.In addition, the test was carried out in the same manner using N-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1,4-benzoxazin-6-yl]cyclohex-1-ene-1,2-dicarboxamid instead of compound (1) as a comparative example.The results are shown in Table 2. Table 2 Table 2Compound (1)50Comparative Compound3Test Example 3: Antibacterial Test on Pythium debaryanumA predetermined amount of compound (1) was dissolved in dimethyl sulfoxide, and the resulting solution was added to a potato extract dextrose agar (PDA) medium so as to give a final concentration of the predetermined concentration.Independently, a bacterial-containing agar piece cut out from the peripheral part of bacterial flora of Pythium debaryanum precultured in a PDA medium free of additives was inoculated on the PDA medium containing compound (1) and cultured at 27°C, and then the stage of mycelium growth was observed. As a result, it could be confirmed that compound (1) had a Pythium debaryanum control effect.Industrial applicabilityCompound (1) is effective against Pythium spp. and is useful for controlling Pythium spp. and protecting crops from Pythium diseases.

Claims

Compound of formula (1): A composition for controlling Pythium spp. comprising the compound according to claim 1 as an active ingredient and a carrier.A method of controlling Pythium spp., wherein an effective amount of the composition of claim 2 is applied to a plant or soil in which the plant grows.