Compounds, their compositions and their use as nematicides - Patent Application 20070122997

Abstract

The present invention relates to a compound of formula (I) JPEG2026507613000103.jpg22170(I) or a pesticidally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, and agricultural compositions thereof, and their use for treating or controlling parasitic nematodes or nematode infestations in agricultural crops.

Description

[Technical Field]

[0001] The present invention relates to compounds having nematicidal activity, agricultural compositions thereof, and the use of such compounds to treat or control parasitic nematodes or nematode infestations in agricultural crops. [Background technology]

[0002] Nematodes are active, flexible, elongated organisms that live on moist surfaces or in liquid environments, including water films in soil and the moist tissues of other organisms. Many species of nematodes have evolved to be highly successful parasites of plants and animals, causing significant economic losses in agriculture. Nematodes are known to affect the yield, growth, and health of crops and plants. Physiological changes in the roots of host plants caused by larval and / or adult nematodes can lead to the formation of galls, which cause the destruction of the vascular system in the plant's roots. Root growth may cease completely, and an inadequate supply of water and nutrients provided by the reduced root system can lead to whitening and / or wilting of leaves and stunted growth, all of which can result in low yield or death. In addition, nematodes can cause physiological effects that increase the susceptibility of plant roots to bacterial and / or fungal attack, including bacteria and / or fungi that the plant would otherwise tolerate. Such attacks can lead to widespread secondary rot and decay. Control of plant parasitic nematodes is therefore crucial to achieving high crop efficiency. Summary of the Invention [Problem to be solved by the invention]

[0003] Despite available treatments, nematodes continue to pose a problem due to the widespread development of resistance to anthelmintics in nematode parasites. There remains a need for new compounds that are more effective, cheaper, less toxic, environmentally safe, or have a different mechanism of action. [Means for solving the problem]

[0004] The present invention relates to a compound of formula (I) [ka] (I) or a pesticidally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof [In the formula, rings A, R 1 and "m" is as defined in the Detailed Description] The present invention further relates to agricultural compositions of compounds of formula (I) and their use for treating or controlling parasitic nematodes or nematode infestations in agricultural crops. DETAILED DESCRIPTION OF THE INVENTION

[0005] (definition) When describing embodiments of the present invention, specific terms are selected for clarity. However, it is not intended that the present invention be limited to the specific terms selected, and it should be understood that such specific terms include all technical equivalents that operate in a similar manner to accomplish the same purpose. Any numerical ranges listed herein are understood to include all subranges encompassed. Also, unless otherwise indicated, the percentages of components in compositions are presented as weight percents.

[0006] The terms "a" or "an," as used herein, are defined as one or more than one. The terms "including" and / or "having," as used herein, are defined as comprising (i.e., open language).

[0007] The term "salt" includes salts prepared from bases or acids, including inorganic or organic bases and inorganic or organic acids. Examples of such salts are acetate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, camsylate, carbonate, chloride, clavulanate, citrate, dihydrochloride, edetate, edisylate, estolate, esylate, fumarate, gluceptate, gluconate, glutamate, glycolylarsanilate, hexylresorcinate, hydrabamine, hydrobromide, hydrochloride, hydroxynaphthoate, iodide, isothioate, lactate, lactobionate, laurate, and the like. Examples of salts derived from inorganic bases include, but are not limited to, salts of malate, maleate, mandelate, mesylate, methyl bromide, methyl nitrate, methyl sulfate, mucoate, napsylate, nitrate, N-methylglucamine ammonium salt, oleate, oxalate, pamoate (embonate), palmitate, pantothenate, phosphate, diphosphate, polygalacturonate, salicylate, stearate, sulfate, acetate, succinate, tannate, tartrate, teoclate, tosylate, triethiodide, and valerate. Examples of salts derived from inorganic bases include, but are not limited to, aluminum, ammonium, calcium, copper, ferric, ferrous, lithium, magnesium, manganic, manganous, potassium, sodium, and zinc.

[0008] As used herein, the wavy line " [ka] " indicates the point of attachment to the rest of the molecule.

[0009] Certain compounds of the present patent application can exist in stereoisomeric forms (e.g., diastereomers and enantiomers) and geometric forms (E and Z configurations). With respect to the overall compounds described by general formula (I), the present patent application extends to these stereoisomeric forms, geometric forms, and mixtures thereof. To the extent that the prior art teaches the synthesis or separation of specific stereoisomers, different stereoisomeric forms of the present patent application may be separated from one another by methods known in the art, or a given isomer may be obtained by stereospecific or asymmetric synthesis. Tautomeric forms and mixtures of the compounds described herein are also contemplated. It is also understood that the compounds of the present invention may exist in solvated (such as hydrated) and unsolvated forms, and that the present invention encompasses all such forms.

[0010] Thus, the present invention provides a compound of formula (I) [ka] (I) wherein [ka] but, [ka] or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein

[0011] Although the compounds of the present invention, or their pesticidally acceptable salts or N-oxides, are suitable for use per se, they will generally be administered in the form of a composition in which one or more compounds are suitably formulated into a composition, usually using at least one agriculturally acceptable excipient.

[0012] Thus, the present invention also includes compositions for treating or controlling parasitic nematodes or nematode infections in plants, comprising an effective amount of one or more compounds of the present invention. In some embodiments, the one or more compounds of the present invention are present in an amount effective to treat or prevent nematode infections in plants.

[0013] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0014] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0015] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0016] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0017] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0018] In one embodiment, the present invention provides a compound of formula (I) [ka] (I) or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, and at least one agriculturally acceptable excipient, wherein: [ka] but, [ka] The present invention provides an agricultural composition comprising:

[0019] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

[0020] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

[0021] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

[0022] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

[0023] In one embodiment, the present invention provides a compound of formula: [ka] or a pesticidally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

[0024] According to certain embodiments, the agricultural composition comprises one or more pesticidally acceptable excipients selected from one or more of surfactants, disintegrants, fillers or carriers or diluents, spreading agents, colorants, anti-caking agents, binders, buffers or pH adjusters or neutralizing agents, pigments, stabilizers, anti-foaming or defoaming agents, penetrating agents, structuring agents, humectants, adhesives, anti-freeze or freezing point depressants, chelating or complexing or sequestering agents, and preservatives. However, those skilled in the art will recognize that additional pesticidally acceptable excipients can be utilized without departing from the scope of the present invention. Pesticide-acceptable excipients are commercially produced and available through various companies.

[0025] According to some embodiments, the surfactant used in the composition of the present invention comprises one or more of an emulsifier, a wetting agent, and a dispersant. According to some embodiments, the surfactant used in the composition comprises one or more of anionic, nonionic, and polymeric surfactants. Anionic surfactants include salts of fatty acids, polycarboxylates, alkyl ether sulfates, alkyl sulfates, alkylaryl sulfates, alkylaryl sulfonates, aryl sulfonates, lignin sulfonates, alkyl diphenyl ether disulfonates, polystyrene sulfonates, salts of alkyl phosphates, alkylaryl phosphates, styrylaryl phosphates, salts of polyoxyethylene alkyl ether sulfates, sodium alpha olefin sulfonates, alkyl benzene sulfonates or their salts, sodium lauroyl sarcosinate, sulfosuccinates, polyacrylates, alkyl ether phosphates, salts of polyoxyethylene alkylaryl phosphates, sulfosuccinate-mono and other diesters, phosphate esters, alkyl naphthalene sulfonates-isopropyl and butyl derivatives; alkylaryl ether phosphoric acid ester ... sodium lauroyl sarcosinate, sulfosuccinate-mono and other diesters, phosphate esters, alkyl naphthalene sulfonates-isopropyl and butyl derivatives; alkylaryl ether phosphoric acid esters, sodium alpha olefin sulfonates, sodium lauroyl sarcosinate, sulfosuccinate-mono and other diesters, phosphate esters, alkyl naphthalene sulfonates-isopropyl and butyl derivatives; alkylaryl ether The surfactants include, but are not limited to, one or more of the following: acid salts, salts of polyoxyethylene aryl ether phosphate esters, mono-alkyl sulfosuccinates, aromatic hydrocarbon sulfonates, ammonium lauryl sulfate, soaps, soap substitutes, sodium alkyl sulfates, sodium dodecyl sulfates, sodium dodecylbenzenesulfonate, sodium laurate, sodium laureth sulfate, sodium nonanoyloxybenzenesulfonate, alkyl carboxylates, sodium stearates, alpha-olefin sulfonates, naphthalenesulfonates, alkylnaphthalenesulfonic acid fatty acid salts, naphthalenesulfonate condensates-sodium salts, fatty alcohol sulfates, alkylnaphthalenesulfonate condensates-sodium salts, naphthalenesulfonic acid condensates condensates-sodium salts, salts of naphthalenesulfonic acid condensed with formaldehyde or alkylnaphthalenesulfonic acid condensed with formaldehyde, or salts or derivatives thereof. However, those skilled in the art will recognize that different anionic surfactants can be used without departing from the scope of the present invention.

[0026] Nonionic or polymeric surfactants include polyol esters, polyol fatty acid esters, ethoxylated and propoxylated fatty alcohols, EO and PO block copolymers, di- and tri-block copolymers; polysorbates, alkyl polysaccharides, polyoxyethylene glycols, sorbitan derivatives, fatty acid esters of sorbitan (spans) and their ethoxylated derivatives (tweens), cocamide monoethanolamine (MEA), decyl, narrow range ethoxylates, oleyl alcohol, PEG-10, polysorbate, polysorbate 20, polysorbate 80, sorbitan, sorbitan monolaurate, sorbitan monostearate, tristearin. The surfactants may be one or more of the following: sorbitan acid, stearyl alcohol, castor oil ethoxylates, polyglycol ethers, polyadducts of ethylene oxide and propylene oxide, polyoxyethylene sorbitan, fatty acid polyglycerides, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene styrylaryl ethers, polyoxyethylene glycol alkyl ethers, alcohol ethoxylates—C6 to C16 / 18 alcohols, linear and branched, alcohol alkoxylates—various hydrophobic materials and EO / PO contents and ratios, polyoxyethylene hydrogenated castor oil, salts or derivatives thereof. However, those skilled in the art will recognize that different nonionic or polymeric surfactants may be utilized without departing from the scope of the present invention.

[0027] According to some embodiments, the dispersant used in the composition includes, but is not limited to, a nonionic dispersant selected from one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, ethoxylated fatty acid, fatty alcohol ethoxylate; alkyl ethoxylate; EO-PO block and graft copolymer.However, those skilled in the art will understand that different nonionic dispersants can be used without departing from the scope of the present invention.

[0028] According to an embodiment, the dispersant used in the composition includes, but is not limited to, anionic dispersants selected from one or more of the following: tristyrylphenol ethoxylate phosphate ester; lignin sulfonate, phenylnaphthalene sulfonate, alkali metal, alkylaryl sulfonate, alkyl sulfonate, the mixture of the sodium salt of naphthalene sulfonic acid urea formaldehyde condensate and the sodium salt of phenolsulfonic acid formaldehyde condensate, polycarboxylate, sodium alkylbenzene sulfonate, the sodium salt of sulfonated naphthalene, sodium naphthalene sulfonate formaldehyde condensate, the condensation product of arylsulfonic acid and formaldehyde, polycyclic aromatic sulfonate, sodium alkylaryl sulfonate and kraft lignin.However, those skilled in the art will understand that different anionic dispersants can be used without departing from the scope of the present invention.

[0029] According to some embodiments, the wetting agent used in the composition includes, but is not limited to, phenol naphthalene sulfonate, alkyl naphthalene sulfonate, sodium alkyl naphthalene sulfonate, sodium naphthalene sulfonate, dibutyl naphthalene sulfonic acid, alkylaryl sulfonate, dioctyl sulfosuccinate, polyoxyethoxylated fatty alcohol, alkane sulfonate, alkyl benzene sulfonate, alkyl ether phosphate, alkyl ether sulfate and alkyl sulfosuccinate monoester, salt, and one or more of their derivatives.However, those skilled in the art will understand that different wetting agents can be used without departing from the scope of the present invention.

[0030] In some embodiments, the carrier used in the composition of the present invention includes, but is not limited to, one or more of solid carriers, fillers, or diluents. In other embodiments, the carrier includes mineral carriers, plant carriers, synthetic carriers, and water-soluble carriers. However, those skilled in the art will understand that different carriers can be used without departing from the scope of the present invention.

[0031] Solid carriers include natural minerals such as clays, such as china clay, acid clay, kaolin, such as kaolinite, dickite, nakruite, and synthetic and diatomaceous silica, mica, such as pyrophyllite, talc, silica, such as cristobalite and quartz, such as attapulgite and sepiolite, vermiculite, laponite, pumice, bauxite, hydrated alumina, perlite, sodium bicarbonate, limestone, natural and synthetic silicates, silica, surface-modified silica, zeolites, diatomaceous earth, loess, mirabilite, white carbon, hydrated lime, synthetic silicic acid, starch, modified starch, cellulose, plant carriers such as cellulose, rice husk, wheat flour, wood flour, starch, rice bran, wheat bran, and soy flour, sodium caseinate, sucrose, salt of sodium, potassium pyrophosphate, sodium tripolyphosphate, or derivatives or mixtures thereof.

[0032] According to some embodiments, the antifoaming or defoaming agent used in the compositions of the present invention includes, but is not limited to, one or more of silica, siloxane, silicon dioxide, polydimethylsiloxane, alkyl polyacrylate, ethylene oxide / propylene oxide copolymer, silicone oil, and magnesium stearate or derivatives thereof. Preferred antifoaming agents include silicone emulsions (e.g., Silicon® SRE from Rhodia, Wacker, or Rhodorsil®), long-chain alcohols, fatty acids, and fluorine-containing organic compounds. However, those skilled in the art will recognize that different antifoaming agents can be used without departing from the scope of the present invention.

[0033] According to certain embodiments, the pH adjuster, buffer, or neutralizer used in the composition includes both organic and inorganic acids and bases, as well as mixtures thereof. According to further embodiments, the pH adjuster, buffer, or neutralizer includes, but is not limited to, one or more of organic acids, inorganic acids, and alkali metal compounds or salts, or derivatives thereof. According to certain embodiments, organic acids include, but are not limited to, citric acid, malic acid, adipic acid, fumaric acid, maleic acid, succinic acid, and tartaric acid, or salts, derivatives thereof, and one or more of the mono-, di-, or tribasic salts of these acids or derivatives thereof. According to certain embodiments, salts of inorganic acids include, but are not limited to, one or more of alkali metal salts, such as sodium chloride, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium monohydrogen phosphate, potassium monohydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, etc. Mixtures can also be used to create the pH adjuster, buffer, or neutralizer. However, those skilled in the art will recognize that different pH adjusters can be used without departing from the scope of the present invention.

[0034] According to certain embodiments, the anti-caking agents used in the composition include, but are not limited to, one or more of polysaccharides, fumed and precipitated silica (white carbon), petroleum resins, Foammaster® soap L sodium stearate, Brij® 700 polyoxyethylene (100) stearyl ether, sodium acetate, sodium metasilicate, sodium alkyl sulfosuccinate, or derivatives thereof. However, one skilled in the art will recognize that different anti-caking agents can be utilized without departing from the scope of the present invention.

[0035] According to certain embodiments, the spreading agent used in the composition includes, but is not limited to, one or more of copolymers of maleic acid and styrene compounds, (meth)acrylic acid copolymers, fatty alcohols, vegetable oils such as cottonseed or mineral oils, petroleum distillates, trisiloxanes and modified trisiloxanes, or derivatives thereof, although one skilled in the art will recognize that different spreading agents can be utilized without departing from the scope of the present invention.

[0036] According to certain embodiments, the binder used in the composition includes, but is not limited to, one or more of paraffin, polyamide resin, polyacrylate, polyoxyethylene, wax, latex, polyvinylpyrrolidone, gums such as xanthan gum, vegetable oils such as cottonseed, or mineral oils, petroleum distillates, modified trisiloxanes, polyglycols, synthetic resin emulsions, or salts or derivatives thereof, however, those skilled in the art will recognize that different binders can be utilized without departing from the scope of the present invention.

[0037] In some embodiments, the structuring agent used in the composition includes, but is not limited to, one or more of a thickening agent, a viscosity modifier, a tackifier, a suspending aid, a rheology modifier, or an anti-settling agent. The structuring agent prevents settling of the active ingredient particles after extended storage.

[0038] According to some embodiments, the structuring agent used in the composition includes, but is not limited to, one or more of: polyacrylic, polysaccharide, cellulose derivative, cellulose derivative, copolymer of polyvinyl alcohol and derivative; clay, for example, kaolin, smectite, attapulgite and gum, for example, guar gum, xanthan gum, gelatin, dextrin, fumed silica, mixture of fumed silica and fumed aluminum oxide, swellable polymer, poly(ethylene glycol), stachyose, cellulose, for example, hemicellulose, carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxy-methylethylcellulose, hydroxyethylpropylcellulose, methylhydroxyethylcellulose, methylcellulose; vegetable starch, for example, corn starch and potato starch.However, those skilled in the art will understand that different structuring agents can be used without departing from the scope of the present invention.

[0039] Preferred structuring agents include one or more of xanthan gum, aluminum silicate, hydroxypropyl methylcellulose, carboxymethylcellulose, methylcellulose, polysaccharides, alkaline earth metal silicates, clay, gelatin, and polyvinyl alcohol.

[0040] According to certain embodiments, the antifreeze or freezing point depressant used in the composition includes, but is not limited to, one or more of polyhydric alcohols, such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, glycerol, monohydric or polyhydric alcohols, glycol ethers, glycerol, although one skilled in the art will recognize that different antifreeze agents may be utilized without departing from the scope of the present invention.

[0041] According to certain embodiments, the chelating or complexing or sequestering agent used in the composition is a polycarboxylic acid, such as polyacrylic acid and various hydrolyzed poly(methyl vinyl ether / maleic anhydride); N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), N,N,N',N'-ethylenediaminetetraacetic acid, N-hydroxyethyl-N,N',N'-ethylenediaminetriacetic acid, and N,N,N',N",N"-diethylenetriaminepentaacetic acid; alpha-hydroxy acids, such as citric acid, tartaric acid, and gluconic acid; orthophosphates, disodium phosphate, monosodium phosphate condensed phosphates, such as sodium tripolyphosphate, tetrasodium pyrophosphate, sodium hexametaphosphate, and sodium tetrapolyphosphate; ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), ethylenediaminediacetic acid (EDDA), ethylenediaminedi(o-hydroxyphenylacetic acid) (EDDHA), cyclohexanediaminetetraacetic acid (CDTA), fulvic acid, urmic acid, nucleic acid, cyclodextrin, humic acid, and pyrophosphate. However, one of ordinary skill in the art will recognize that different chelating agents can be utilized without departing from the scope of the present invention.

[0042] According to some embodiments, the penetrant used in the composition includes, but is not limited to, one or more of alcohol, glycol, glycol ether, ester, amine, alkanolamine, amine oxide, quaternary ammonium compound, triglyceride, fatty acid ester, fatty acid ether, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, or dimethyl sulfoxide, polyoxyethylene trimethylolpropane monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene trimethylolpropane dioleate, polyoxyethylene trimethylolpropane trioleate, polyoxyethylene sorbitol hexaoleate. However, those skilled in the art will understand that different penetrants can be used without departing from the scope of the present invention.

[0043] According to some embodiments, the moisturizer is selected from one or more of polyoxyethylene / polyoxypropylene copolymers, particularly block copolymers, but not limited to these.Other moisturizers are propylene glycol, monoethylene glycol, hexylene glycol, butylene glycol, ethylene glycol, diethylene glycol, poly(ethylene glycol), poly(propylene glycol), glycerol, etc.; polyhydric alcohol compounds such as propylene glycol ethers, and their derivatives.However, those skilled in the art will understand that different moisturizers can be used without departing from the scope of the present invention.

[0044] According to certain embodiments, stabilizers used in agricultural compositions include, but are not limited to, one or more of peroxide compounds, such as hydrogen peroxide and organic peroxides, zeolites, antioxidants, such as phenolic compounds, phosphate compounds, EDTA, sodium sulfite, citric acid, citrate salts, etc. However, one skilled in the art will recognize that other conventionally known stabilizers may be utilized without departing from the scope of the present invention.

[0045] According to certain embodiments, the preservatives are formic acid and derivatives of 2H-isothiazol-3-ones (so-called isothiazolone derivatives), such as alkylisothiazolones (e.g. 2-methyl-2H-isothiazol-3-one, MIT; chloro-2-methyl-2H-isothiazol-3-one, CIT), benzisothiazolones (e.g. 1,2-benzisothiazol-3(2H)-one, BIT, commercially available as Proxel® from Arch Biocides Ltd.) or 2-methyl-4,5-trimethylene-2H-isothiazol-3-one (MTIT), Proxel® from Arch Biocides Ltd. or Acticide® RS from Thor Chemie and Kathon® MK from Lanxess, sodium propionate (Sodium The preservatives may be selected from one or more of the following: sodium benzoate, propylparaben, sodium propylparaben (Sodium), potassium sorbate, potassium benzoate, phenylmercuric nitrate, phenylethyl alcohol, sodium, ethylparaben, methylparaben, butylparaben, benzyl alcohol, benzethonium chloride, and cetylpyridinium chloride; and the antioxidants may include, but are not limited to, one or more of imidazole and imidazole derivatives (e.g., urocanic acid), 4,4'-thiobis-6-t-butyl-3-methylphenol, 2,6-di-t-butyl-p-cresol (BHT), pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate; and amine antioxidants. However, those skilled in the art will recognize that other conventional preservatives may be utilized without departing from the scope of the present invention.

[0046] According to certain embodiments, pigments and colorants are selected from, but are not limited to, synthetic chemicals obtained from various manufacturers. Pigments and colorants can be in lake form and water-soluble or water-insoluble. Dyes can be solvent dyes, acid dyes, or basic dyes. Examples of such products include, but are not limited to, Unisperse Red 3855, Pigmosol Agro Red 3785, and Pigment 15. However, one skilled in the art will recognize that other conventionally known pigments and colorants can be utilized without departing from the scope of the present invention.

[0047] According to some embodiments, the disintegrants used in agricultural compositions include, but are not limited to, inorganic water-soluble salts, such as sodium chloride; water-soluble organic compounds, such as agar, hydroxypropyl starch, carboxymethyl starch ether, tragacanth, cross-linked sodium carboxymethylcellulose, sodium tripolyphosphate, sodium hexametaphosphate, metal stearates, cellulose powder, dextrin, methacrylate copolymer, Polyplasdone® XL-10 (cross-linked polyvinylpyrrolidone), and poly(vinylpyrrolidone).However, those skilled in the art will understand that other conventionally known disintegrants can be used without departing from the scope of the present invention.

[0048] According to certain embodiments, the binding agents or binders used in the agricultural compositions include, but are not limited to, one or more of maltodextrin, carbohydrates, including mono-, di-, oligo-, and polysaccharides, complex organic substances, synthetic organic polymers, or derivatives and combinations thereof, although one skilled in the art will recognize that other conventionally known binding agents may be utilized without departing from the scope of the present invention.

[0049] According to certain embodiments, the pesticidally acceptable excipient is present in the range of 0.1% w / w to 98% w / w of the total composition. According to further embodiments, the pesticidally acceptable excipient is present in the range of 0.1% w / w to 95% w / w of the total composition.

[0050] According to certain embodiments, the agricultural composition is in the form of a solid or liquid or gel or paste.

[0051] According to certain embodiments, solid agricultural compositions can include powders, granules, and dusts.

[0052] According to some embodiments, the agricultural composition may be in the form of a powder, including wettable powder and dispersible powder. According to some embodiments, the composition may be in the form of a granule, including broadcast granule, water disintegrable granule, spheronized granule, pellet, extruded granule, and water dispersible granule.

[0053] According to certain embodiments, the composition is preferably in the form of water-dispersible granules, wettable powders, sprinkling granules, water-disintegrating granules or spherical granules.

[0054] According to certain embodiments, the composition is a solid composition, preferably in the form of granules including spherical granules, extruded granules, water-disintegrating granules, wettable powders, water-dispersible granules, dustable powders (DP), powders for dry seed treatment (DS), water-disintegrating tablets or water-dispersible powders for slurry seed treatment (WS).

[0055] According to some embodiments, the liquid composition may comprise a suspension, emulsion, liquid suspension, flowable concentrate, emulsifiable concentrate, seed dressing, suspoemulsion, or emulsion in water. In further embodiments, in the liquid composition, the compound of the present invention may be present in suspended, emulsified, or dissolved form. Examples of particularly suitable formulations are solutions, soluble concentrates (e.g., SL, LS), dispersible concentrates (DC), suspensions and suspension concentrates (e.g., SC, oil dispersion (OD), OF, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, microemulsions (ME), and suspoemulsions (SE), suspension concentrates for seed treatment (FS), and ultra low volume (ULV).

[0056] According to certain embodiments, the liquid composition may comprise a liquid suspension or suspension concentrate (SC); a suspoemulsion (SE), an oil dispersion (OD), a flowable concentrate (FC), or a seed treatment suspension concentrate (FS), ultra-low volume (ULV).

[0057] According to some embodiments, the particle size of the composition is in the range of 0.1 microns to 50 microns. According to some embodiments, the composition is in the form of granules in the size range of 0.025 to 6 mm.

[0058] According to one embodiment, the composition is in the form of spherical granules or scatter granules or water-disintegrating granules or extruded granules, wherein the granules are in the size range of 0.025 to 6 mm.

[0059] According to one embodiment, the granules are dispersed into particles within the size range of 0.1 microns to 50 microns.

[0060] In one embodiment, the present invention provides an agricultural composition comprising a compound of the present invention in the range of 1% w / w to 95% w / w of the total composition and at least one pesticidally acceptable excipient in the range of 1% w / w to 99% w / w of the total composition, wherein the particles are present in the size range of 0.1 microns to 50 microns.

[0061] In one embodiment, the present invention provides an agricultural composition comprising a compound of the present invention in the range of 1% w / w to 95% w / w of the total composition and at least one pesticidally acceptable excipient in the range of 1% w / w to 99% w / w of the total composition, wherein the particles are present in the size range of 0.1 microns to 50 microns and the granules are in the size range of 0.025 to 6 mm.

[0062] According to one embodiment, the present invention relates to a process for preparing an agricultural composition of the present invention comprising a compound of the present invention present in the range of 1% w / w to 95% w / w of the total composition and at least one pesticidally acceptable excipient present in the range of 1% w / w to 99% w / w of the total composition.

[0063] In certain embodiments, the present invention includes a method of treating or controlling a parasitic nematode or nematode infection in a plant, comprising administering one or more compounds of the present invention.

[0064] In certain embodiments, the present invention includes a method of treating or controlling parasitic nematodes or nematode infections in plants, comprising administering a composition of one or more compounds of the present invention.

[0065] In another embodiment, the present invention also includes the use of one or more compounds of the present invention to treat or control parasitic nematodes or nematode infestations in plants.

[0066] In another embodiment, the present invention also includes the use of a composition of one or more compounds of the present invention to treat or control parasitic nematodes or nematode infestations in plants.

[0067] The present invention also includes the use of a composition of one or more compounds of the present invention in the preparation of a medicament for treating or controlling a parasitic nematode or nematode infestation in a plant.

[0068] In one embodiment, the present invention provides a method for treating or controlling a parasitic nematode or nematode infection in a plant, comprising administering to a plant a compound of formula (I) [ka] (I) or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: [ka] teeth, [ka] is] The method includes administering

[0069] In one embodiment, the present invention provides a method for treating or controlling a parasitic nematode or nematode infection in a plant, comprising administering to a plant a compound of the formula: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0070] In one embodiment, the present invention provides a method for treating or controlling a parasitic nematode or nematode infection in a plant, comprising the step of: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0071] In one embodiment, the present invention provides a method for treating or controlling a parasitic nematode or nematode infection in a plant, comprising the step of: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0072] In one embodiment, the present invention provides a method for treating or controlling a parasitic nematode or nematode infection in a plant, comprising the step of: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0073] In one embodiment, the present invention provides a method for treating or controlling a parasitic nematode or nematode infection in a plant, comprising the step of: [ka] or a pesticidally acceptable salt or N-oxide thereof.

[0074] In another embodiment, the present invention relates to the use of an agricultural composition for treating or controlling a parasitic nematode or nematode infestation in a plant, wherein the composition comprises a compound of formula (I) [ka] (I) or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, and at least one agriculturally acceptable excipient; During the ceremony, [ka] but, [ka] Provides for use.

[0075] In another embodiment, the present invention provides the use of an agricultural composition for treating or controlling a parasitic nematode or nematode infestation in a plant, wherein the composition comprises a compound of the formula: [ka] or an agriculturally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

[0076] Nematodes include parasitic nematodes such as root-knot, cyst, and lesion nematodes. The term "nematodes" encompasses eggs, larvae, nymphs, and adult forms of nematodes. Parasitic nematodes include the root-knot nematodes Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria, and other Meloidogyne species; the cyst-forming nematodes Globodera rostochiensis and other Globodera species; the wheat cyst nematode Heterodera avenae, soybean cyst nematode Heterodera glycines, sugar beet cyst nematode Heterodera schachtii, and clover cyst nematode Heterodera trifolii, and other Heterodera species; seed-knot nematodes, Anguina species; stem and leaf nematodes, Aphelenchoides species; stinging nematodes, Eelonolaimus longicaudatus and other Belonolaimus species; and pinewood nematodes, Bursaphelenchus xylophilus. xylophilus and other Bursaphelenchus species; ring nematodes, such as Criconema species, Criconemella species, Criconemoides species, and Mesocriconema species; stem and bulb nematodes, such as Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; awl nematodes, such as Dolichodorus species;spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; lance nematodes, Hoploaimus species; pseudo-root-knot nematodes, Nacobbus species; needle nematodes, Longidorus elongatus elongatus and other Longidorus species; pin nematodes, Pratylenchus species; lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; burrowing nematodes, Radopholus similis and other Radopholus species; nephromorph nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; the stag beetle nematodes Trichodorus primitivus and other Trichodorus and Paratrichodorus species; the dwarf nematodes Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species;Citrus root nematodes, such as Tylenchulus species; dagger nematodes, such as Xiphinema species; and other plant parasitic nematode species, such as, but not limited to, Subanguina species, Hypsoperine species, Macroposthonia species, Melinius species, Punctodera species, and Quinisulcius species.

[0077] In the context of treating or controlling parasitic nematodes or nematode infections in plants, an effective amount of one or more compounds of the present invention is, for example, an amount that reduces the amount of nematode infection in a plant compared to the amount of nematode infection in a plant without the administration of one or more compounds of the present application. The reduction in infection can be assessed, for example, by detecting the amount of viable or living nematodes in the plant and / or by observing or assessing the extent of the disease, disorder, or condition caused by the nematode infection.

[0078] The dosage of one or more compounds of the present invention in a plant will vary depending on many factors, such as its pharmacodynamic properties, mode of administration, age, health and weight / mass of the plant, nature and extent of symptoms, frequency of treatment and type of concomitant treatment, if any, etc. The one or more compounds of the present invention may be initially administered at a suitable dosage that can be adjusted as needed depending on the response.

[0079] In some embodiments, one or more compounds of the present invention are applied to the plant at any suitable rate, the selection of which can be made by one of ordinary skill in the art. Factors to consider include, for example, plant identification, nematode identification, plant disease, disorder or condition identification, severity of nematode infection, severity of plant disease, disorder or condition, plant age, activity of one or more compounds of the present application and concentration of one or more compounds of the present application, or a combination thereof.

[0080] In some embodiments, the leaves of the plant and / or the soil surrounding the plant are contacted with one or more compounds of the present application.

[0081] In some embodiments, the nematode infects the plant and one or more compounds are administered to the soil or to the plant. In some embodiments, the one or more compounds are administered to the soil before planting. In some embodiments, the one or more compounds are administered to the soil after planting. In some embodiments, the one or more compounds are administered to the soil using a drip system. In some embodiments, the one or more compounds are administered to the soil using an irrigation system. In some embodiments, the one or more compounds are administered to the roots of the plant or to the foliage (e.g., leaves, stems) of the plant. In some embodiments, the one or more compounds are tilled into the soil or administered in furrows. In some embodiments, the one or more compounds are administered to seeds. In some embodiments, the one or more compounds are applied as a seed coating.

[0082] In certain embodiments, the present invention also provides a method for protecting seeds from parasitic nematodes, the method comprising contacting seeds with an effective amount of a compound of formula (I) or a pesticidally acceptable salt or N-oxide thereof (e.g., as a composition described herein).

[0083] Furthermore, the compositions of the present invention are suitable for drip or sprinkler irrigation, in addition to other methods of application of agricultural compositions.

[0084] According to certain embodiments, specifically provided are compounds of formula (I) that exhibit a greater than 90% reduction in nematode populations compared to untreated controls at concentrations such as 100, 200, 250, 300, 500 or 1000 ppm.

[0085] According to certain embodiments, specifically provided are compounds of formula (I) that exhibit a greater than 80% reduction in nematode populations compared to untreated controls at concentrations such as 100, 200, 250, 300, 500 or 1000 ppm.

[0086] According to certain embodiments, specifically provided are compounds of formula (I) that exhibit a greater than 50% reduction in nematode populations compared to untreated controls at concentrations such as 100, 200, 250, 300, 500 or 1000 ppm.

[0087] In some embodiments, the nematodes are infecting the plants and one or more compositions are administered to the soil or to the plants. In some embodiments, one or more compositions are administered to the soil before planting. In some embodiments, one or more compositions are administered to the soil after planting. In some embodiments, one or more compositions are administered to the soil using a drip system. In some embodiments, one or more compositions are administered to the soil using an irrigation system. In some embodiments, one or more compositions are administered to the roots of the plants or to the foliage (e.g., leaves, stems) of the plants. In some embodiments, one or more compositions are tilled into the soil or administered in furrows. In some embodiments, one or more compositions are administered to seeds.

[0088] In certain embodiments, the method of application includes administering one or more compositions of the present application via a means selected from, but not limited to, pre-planting, post-planting, as a feed additive, drench, and external application.

[0089] In certain embodiments, the term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

[0090] In certain embodiments, the plant is a cultivated plant. In some embodiments, the plant is a crop plant. In further embodiments, plants include, but are not limited to, soybeans, cotton, flax, hemp, jute, corn, tobacco, nuts, almonds, coffee, tea, pepper, grape vines, hops, wheat, barley, rye, oats, rice, maize, sorghum, apples, pears, plums, peaches, bananas, plantains, cherries, strawberries, raspberries, blackberries, beans, lentils, peas, soybeans, rapeseed, mustard, poppy, olives, sunflowers, coconuts, castor, cocoa, peanuts, spinach, asparagus, lettuce, cabbage, carrots, onions, tomatoes, potatoes, peppers, cucumbers, melons, pumpkins, sugarcane, sugar beets, fodder beets, avocados, cinnamon, camphor, oranges, mandarins, lemons, limes, grapefruit, rubber trees, ornamentals, and / or turfgrasses.

[0091] (Preparation method) The compounds and specific examples described herein, including compounds of general formula (I), are prepared via the reaction sequence depicted in Scheme 1 using techniques known to those skilled in the art. Furthermore, where specific substrates, reagents, solvents, etc. are referred to in the schemes, it is understood that other suitable substrates, reagents, etc. may be used and are within the scope of the present invention. Variations to reaction conditions, e.g., temperature, reaction duration, or combinations thereof, are contemplated as part of the present invention. Compounds obtained by using the general reaction sequence may be of insufficient purity. These compounds can be purified by any method known to those skilled in the art for purifying organic compounds, such as crystallization or silica gel or alumina column chromatography using different solvents in appropriate ratios. All possible stereoisomers are contemplated within the scope of the present invention.

[0092] Scheme 1: [ka] Scheme 1

[0093] A compound of general formula (I) may be prepared by reacting a compound of formula (A) or a salt thereof with a compound of formula (B) or a salt thereof, as shown in Scheme 1. The reaction may be carried out in the presence or absence of a suitable base. The reaction may be carried out in the presence of a solvent or mixture of solvents at a suitable temperature range, for example, between −10° C. and 100° C., to yield a compound of general formula (I). Suitable solvents include, but are not limited to, water, alcohol (methanol, ethanol, n-propanol, iso-propanol, n-butanol, or iso-butanol), tetrahydrofuran, ethyl acetate, and acetonitrile, or mixtures thereof. Suitable bases may include, but are not limited to, organic bases (e.g., trimethylamine or diisopropylethylamine). Suitable bases may include, but are not limited to, inorganic bases (e.g., LiOH, NaOH, NaHCO3, Na2CO3, KOH, KHCO3, K2CO3, Cs2CO3, or CsOH). [Example]

[0094] Example 1: (E)-N 2 Preparation of -{[2-(trifluoromethyl)phenyl]methylidene}-L-arginine> [ka] 2-Trifluoromethylbenzaldehyde (1 g) was added to a slurry of L-arginine (0.95 g) in ethanol (25 ml), and the mixture was stirred at room temperature for 6 hours. The resulting solid was filtered, washed with n-hexane (20 ml), and dried under high vacuum to give 1.08 g of ((E)-N2-{[2-(trifluoromethyl)phenyl]methylidene}-L-arginine as a solid. 1H NMR(400MHz,DMSO-d6)δ1.40~1.51(m,2H), 1.69~1.74(m,1H), 1.91~1.94(m,1H), 3.08~3.09(m,2H), 3.77(t,J=6.8Hz,1H), 7.40~8.00(brs,4 H), 7.63(t,J=7.2Hz,1H), 7.72(t,J=7.6Hz,1H), 7.78(d,J=7.6Hz,1H), 8.16(d,J=7.6Hz,1H), 8.52(d,J=2.4Hz,1H), 9.44(s,1H);ESI-MS:m / z 331.10(M+H)+.

[0095] Example 2: (E)-N 2 Preparation of -{[3-(trifluoromethyl)phenyl]methylidene}-L-arginine> [ka] 3-Trifluoromethylbenzaldehyde (1 g) was added to a slurry of L-arginine (0.95 g) in ethanol (15 ml), and the mixture was stirred at room temperature for 5 hours. n-Hexane (15 ml) was added to the mixture, which was stirred at room temperature for an additional 2 hours. The resulting solid was filtered, washed with n-hexane (10 ml), and dried under high vacuum to give 1.59 g of ((E)-N 2 -{[3-(trifluoromethyl)phenyl]methylidene}-L-arginine was obtained as a solid. 1H NMR(400MHz,DMSO-d6)δ1.47~1.52(m2H), 1.68~1.73(m,1H), 1.90~1.94(m,1H), 3.80~3.12(m,2H), 3.75(t,J=6.8Hz,1H), 7.20~7.90(br s,4H), 7.71(t,J=7.6Hz,1H), 7.77(d,J=8.0Hz,1H), 8.01(d,J=7.6Hz,1H), 8.05(s,1H), 8.35(s,1H), 9.39(br s,1H);ESI-MS:m / z 331.10(M+H)+.

[0096] Example 3: (E)-N 2 Preparation of -[(4-chloro-2-hydroxyphenyl)methylidene]-L-arginine [ka] L-arginine (1.07 g) was added to a solution of 4-chloro-2-hydroxybenzaldehyde (1.0 g) in ethanol (20 ml), and the reaction mixture was stirred at room temperature for 18 hours. The resulting solid was filtered, washed with n-hexane (20 ml), and dried under high vacuum to give 1.28 g of (E)-N 2 -[(4-chloro-2-hydroxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.44~1.51(m,2H), 1.75~1.91(m,2H), 3.08~3.10(m,2H), 3.91(t,J=6.4Hz,1H), 6.54(dd,J=2.0,6.4Hz ,1H), 6.65(d,J=1.6Hz,1H), 7.28(d,J=8.4Hz,1H), 7.44(brs,4H), 8.41(brs,1H), 9.39(brs,1H), 14.53(brs,1H);ESI-MS:m / z 313.10(M+H) + .

[0097] Example 4: (E)-N 2 Preparation of -[(6-chloro-2-hydroxyphenyl)methylidene]-L-arginine [ka] L-arginine (1.07 g) was added to a solution of 6-chloro-2-hydroxybenzaldehyde (1.0 g) in ethanol (20 ml), and the reaction mixture was stirred at room temperature for 4 hours. The solid was filtered, washed with n-hexane (20 ml), and dried under high vacuum to give 1.64 g of (E)-N 2 -[(6-chloro-2-hydroxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.45~1.54(m,2H), 1.76~1.95(m,2H), 3.10~3.16(m,2H), 4.06(t,J=6.4Hz,1H), 6.64~6.67(m ,2H), 7.22(dd,J=0.4,8.0Hz,1H), 7.55(brs,4H), 8.72(d,J=5.6Hz,1H), 9.33(brs,1H), 15.25(brs,1H);ESI-MS:m / z 313.50(M+H) + .

[0098] Example 5: (E)-N 2 Preparation of -[(3-fluoro-2-hydroxyphenyl)methylidene]-L-arginine [ka] 3-Fluoro-2-hydroxybenzaldehyde (1 g) was added to a slurry of L-arginine (1.18 g) in ethanol (20 ml), and the mixture was stirred at room temperature for 4 hours. The resulting solid was filtered, washed with n-hexane (20 ml), and dried under high vacuum to give 1.54 g of (E)-N 2 -[(3-fluoro-2-hydroxyphenyl)methylidene]-L-arginine was obtained as a solid. 1H NMR(400MHz,DMSO-d6)δ1.46~1.76(m,2H), 1.78~1.96(m,2H), 3.10~3.20(m,2H), 3.96(t,J=6.8Hz,1H), 6.34 ~6.39(m,1H), 7.04~7.48(m,2H), 7.25~8.0(brs,4H), 8.44(s,1H), 9.35(s,1H), 14.40(brs,1H);ESI-MS:m / z 297.20(M+H)+.

[0099] Example 6: (E)-N 2 Preparation of -[(4-fluoro-2-hydroxyphenyl)methylidene]-L-arginine [ka] 4-Fluoro-2-hydroxy-benzaldehyde (1 g) was added to a slurry of L-arginine (1.18 g) in ethanol (25 ml) and stirred at room temperature under nitrogen for 3 hours. The reaction mixture was then filtered, washed with n-hexane (10 ml), and dried under high vacuum to give 1.36 g of (E)-N 2 -[(4-fluoro-2-hydroxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.48~1.51(m,2H), 1.76~1.90(m,2H), 3.09~3.11(m,2H) , 3.91(t,J=6.0Hz,1H), 6.28~6.35(m,2H), 7.29(t,J=8.4Hz,1H), 7.20~7.80(br s,4H), 8.36(s,1H), 9.36(s,1H), 14.45(s,1H); ESI-MS: m / z 297.10(M+H)+.

[0100] Example 7: (E)-N 2 Preparation of -[(5-fluoro-2-hydroxyphenyl)methylidene]-L-arginine [ka] 5-Fluoro-2-hydroxybenzaldehyde (1 g) was added to a slurry of L-arginine (1.18 g) in ethanol (20 ml), and the mixture was stirred at room temperature for 5 hours. The solid was then filtered, washed with n-hexane (20 ml), and dried under high vacuum to give 1.57 g of (E)-N 2 -[(5-fluoro-2-hydroxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.46~1.51(m,2H), 1.70~1.76(m,1H), 1.89~1.93(m,1H), 3.07~3.09(m,2H), 3.78(t,J=6.4Hz,1H), 6.8 0~6.84(m,1H), 7.12~7.18(m,1H), 7.26~7.29(m,1H), 7.30~7.90(brs,4H), 8.42(s,1H), 9.57(s,1H), 14.06(s,1H);ESI-MS:m / z 297.40(M+H)+.

[0101] Example 8: (E)-N 2 Preparation of -[(6-fluoro-2-hydroxyphenyl)methylidene]-L-arginine [ka] 6-Fluoro-2-hydroxy-benzaldehyde (1 g) was added to a slurry of L-arginine (1.18 g) in ethanol (25 ml), which was stirred at room temperature under nitrogen for 3 hours. The solid was filtered, washed with n-hexane (10 ml), and dried under high vacuum to give 1.61 g of (E)-N 2 -[(6-fluoro-2-hydroxyphenyl)methylidene]-L-arginine was obtained as a solid. 1H NMR(400MHz,DMSO-d6)δ1.46~1.49(m,2H), 1.74~1.80(m,1H), 1.87~1.94(m,1H), 3.09~3.11(m,2H), 4.00(t, J=6.0Hz,1H), 6.31~6.36(dd,J=7.6,2.4Hz,1H), 6.48(d,J=8.8Hz,1H), 7.23(dd,J=8.4,7.6Hz,1H), 7.42(br s,4H), 8.60(d,J=4.8Hz,1H), 9.40(s,1H), 14.75(s,1H);ESI-MS:m / z 297.40(M+H) + .

[0102] Example 9: (E)-N 2 Preparation of -[(2-hydroxy-3-methoxyphenyl)methylidene]L-arginine [ka] Ortho-vanillin (4.59 g) was added to a slurry of L-arginine (5.0 g) in ethanol (25 ml), which was stirred at room temperature under a nitrogen atmosphere for 6 hours. N-hexane (50 ml) was added to the reaction mixture, which was stirred at room temperature for 1 hour. The product was filtered, washed with n-hexane (50 ml), and dried under high vacuum to give 9.10 g of ((E)-N 2 -[(2-hydroxy-3-methoxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.49~1.59(m,2H), 1.71~1.80(m,1H), 1.88~1.93(m,1H), 3.05~3.15(m, 2H), 3.73(s,3H), 3.85(t,J=6.4Hz,1H), 6.55(t,J=8.0Hz,1H), 6.87~6.89(m,2H), 7.20~8.01(br s,4H), 8.36(s,1H), 9.53(br s,1H), 14.25(br s,1H);ESI-MS:m / z 309.10(M+H) + .

[0103] Example 10: (E)-N 2Preparation of -[(2-hydroxy-5-methoxyphenyl)methylidene]-L-arginine [ka] L-arginine (1.09 g) was added to a solution of 2-hydroxy-5-methoxybenzaldehyde (1.0 g) in ethanol (25 ml), and the reaction mixture was stirred at room temperature for 2 hours. The solid was filtered, washed with n-hexane (25 ml), and dried under high vacuum to give 1.57 g of (E)-N 2 -[(2-hydroxy-5-methoxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.46~1.51(m,2H), 1.69~1.74(m,1H), 1.90~1.95(m,1H), 3.05~3.10(m,2H), 3.33(s,3H), 3.75(t,J=6.4Hz,1H) , 6.76(d,J=8.8Hz,1H), 6.90(dd,J=2.8,6.0Hz,1H), 7.00(s,1H), 7.44(brs,4H), 8.40(s,1H), 9.51(brs,1H), 13.56(s,1H);ESI-MS:m / z 309.20(M+H) + .

[0104] Example 11: (E)-N 2 Preparation of -[(2-hydroxy-6-methoxyphenyl)methylidene]-L-arginine [ka] L-arginine (1.09 g) was added to a solution of 2-hydroxy-6-methoxybenzaldehyde (1.0 g) in ethanol (25 ml), and the reaction mixture was stirred at room temperature for 18 hours. The solid was filtered, washed with n-hexane (25 ml), and dried under high vacuum to give 1.03 g of (E)-N 2 -[(2-hydroxy-6-methoxyphenyl)methylidene]-L-arginine was obtained as a solid. 1H NMR(400MHz,DMSO-d6)δ1.40~1.51(m,2H), 1.68~1.77(m,1H), 1.85~1.90(m,1H), 3.00~3.10(m,2H), 3.78(s,3H), 3.88(t,J=6.4Hz,1H), 6. 12(d,J=8.0Hz,1H), 6.24(d,J=8.8Hz,1H), 7.16(t,J=8.0Hz,1H), 7.60(brs,4H), 8.59(s,1H), 9.47(brs,1H), 14.84(brs,1H);ESI-MS:m / z 309.10(M+H) + .

[0105] Example 12: (E)-N 2 Preparation of -[(2,4-dihydroxy-6-methylphenyl)methylidene]-L-arginine [ka] L-arginine (1.09 g) was added to a solution of 2,4-dihydroxy-6-methylbenzaldehyde (1.0 g) in ethanol (20 ml), and the reaction mixture was stirred at room temperature for 12 hours. The solid was filtered, washed with n-hexane (25 ml), and dried under high vacuum to give 0.91 g of (E)-N 2 -[(2,4-Dihydroxy-6-methylphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.45~1.55(m,2H), 1.68~1.95(m,2H), 2.20(s,3H), 3.05~3.14(m,2H), 3.91(t,J=6. 4Hz,1H), 6.50(s,1H), 7.01(s,1H), 7.60(brs,4H), 8.59(s,1H), 9.47(brs,1H), 14.84(brs,1H);ESI-MS:m / z 309.20(M+H) + .

[0106] Example 13: (E)-N 2 Preparation of -[(2,4-dimethoxyphenyl)methylidene]-L-arginine [ka] L-arginine (1 g) was added to a solution of 2,4-dimethoxybenzaldehyde (1.0 g) in ethanol (25 ml), and the reaction mixture was stirred at room temperature for 16 hours. The solid was filtered, washed with n-hexane (50 ml), and dried under high vacuum to give 1.70 g of (E)-N 2 -[(2,4-Dimethoxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.48~1.62(m,3H), 1.80~1.91(m,1H), 3.03~3.07(m,2H), 3.60(t,J=6.4Hz,1H), 3.80(s,3H), 3.87 (s,3H), 6.54~6.59(m,2H), 7.04(brs,2H), 7.75(d,J=8.4Hz,1H), 7.90(brs,2H), 8.44(s,1H), 9.50(brs,1H);ESI-MS:m / z 323.30(M+H) + .

[0107] Example 14: (E)-N 2 Preparation of -{[2-hydroxy-5-(trifluoromethoxy)phenyl]methylidene}-L-arginine [ka] L-arginine (0.81 g) was added to a solution of 2-hydroxy-5-(trifluoromethoxy)benzaldehyde (1.0 g) in ethanol (20 ml), and the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was concentrated under vacuum and then crystallized in a mixture of ethanol and n-hexane to give 1.21 g of (E)-N 2 -{[2-hydroxy-5-(trifluoromethoxy)phenyl]methylidene}-L-arginine was obtained as a solid. 1H NMR(400MHz,DMSO-d6)δ1.47~1.51(m 2H), 1.74~1.80(m,1H), 1.91~1.96(m,1H), 3.00~3.11(m,2H), 3.85(t,J=6.4Hz,1H), 6.83(d,J=9.2Hz,1H) , 7.26~7.28(m,1H), 7.43(s,1H), 7.80(brs,4H), 8.48(s,1H), 9.48(brs,1H), 14.56(brs,1H);ESI-MS:m / z 363.30(M+H) + .

[0108] Example 15: (E)-N 2 Preparation of -[(3-chloro-5-fluoro-2-hydroxyphenyl)methylidene]-L-arginine [ka] L-arginine (0.95 g) was added to a solution of 3-chloro-5-fluoro-2-hydroxybenzaldehyde (1.0 g) in ethanol (25 ml), and the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was filtered, washed with n-hexane (25 ml), and dried under high vacuum to give 1.37 g of (E)-N 2 -[(3-chloro-5-fluoro-2-hydroxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.48~1.55(m 2H), 1.79~1.94(m,2H), 3.10~3.15(m,2H), 4.00(t,J=6.4Hz,1H), 7.12(dd,J=3.2,5.6Hz,1H), 7.4 9(dd,J=3.2,5.2Hz,1H), 7.64(brs,4H), 8.45(s,1H), 9.31(brs,1H), 14.50(brs,1H);ESI-MS:m / z 331.60(M+H) + .

[0109] Example 16: (E)-N 2 Preparation of -[(4-methoxyphenyl)methylidene]-L-arginine [ka] Anisaldehyde (7.82 g) was added to a solution of L-arginine (10 g) in water (80 ml), and the mixture was stirred at room temperature for 7 hours. The solid was filtered, washed with water (50 ml), and dried under high vacuum to give 16.6 g of (E)-N 2 -[(4-Methoxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR (400MHz, DMSO-d6) δ1.40~1.54(m,2H), 1.64~1.69(m,1H), 1.85~1.90(m,1H), 3.08~3.09(m,2H) ), 3.65(t,J=6.0Hz,1H), 3.77(s,3H), 6.95(d,J=8.4Hz,2H), 7.64(d,J=8.4Hz,2H), 7.40~8.15(br s,4H), 8.16(s,1H), 9.25(br s,1H);ESI-MS:m / z 293.20(M+H) + .

[0110] Example 17: (E)-N 2 Preparation of -[(3-hydroxy-4-methoxyphenyl)methylidene]-L-arginine [ka] L-arginine (1.09 g) was added to a solution of iso-vanillin (1.0 g) in ethanol (25 ml), and the reaction mixture was stirred at room temperature for 5 hours. The solid was filtered, washed with n-hexane (50 ml), and dried under high vacuum to give 0.86 g of (E)-N 2 -[(3-hydroxy-4-methoxyphenyl)methylidene]-L-arginine was obtained as a solid. 1H NMR(400MHz,DMSO-d6)δ1.40~1.52(m,2H), 1.62~1.40(m,1H), 1.83~1.91(m,1H), 3.02~3.06(m,2H), 3.62(t,J=6.4Hz,1H), 3.44(b rs,1H), 3.86(s,3H), 6.92(d,J=8.4Hz,1H), 7.02(d,J=9.6Hz,1H), 7.23(d,J=1.2Hz,1H), 7.60(brs,5H), 8.06(s,1H);ESI-MS:m / z 309.10(M+H) + .

[0111] Example 18: (E)-N 2 Preparation of -[(3-chloro-4-methoxyphenyl)methylidene]-L-arginine [ka] 3-Chloro-p-anisaldehyde (1.5 g) was added to a slurry of L-arginine (1.45 g) in ethanol (30 ml), and the mixture was stirred at room temperature for 16 hours. n-Hexane (60 ml) was added to the reaction mixture, which was stirred for an additional hour. The solid was filtered, washed with n-hexane (30 ml), and dried under high vacuum to give 1.68 g of (E)-N 2 -[(3-chloro-4-methoxyphenyl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.41~1.51(m,2H), 1.66~1.69(m,1H), 1.85~1.88(m,1H), 3.01~3.10(m,2H), 3.66(t,J=6.4Hz,1H), 3.89(s,3H), 7.1 8(d,J=8.4Hz,1H), 7.56(brs,2H), 7.63(dd,J=1.6,6.8,1H), 7.77(d,J=1.6Hz,1H), 7.95(brs,2H), 8.16(s,1H), 9.32(brs.1H);ESI-MS:m / z 349.60(M+Na) + .

[0112] Example 19: (E)-N 2Preparation of -{[4-(methylsulfanyl)phenyl]methylidene}-L-arginine [ka] L-arginine (1.09 g) was added to a solution of 4-(methylthio)benzaldehyde (1.0 g) in ethanol (40 ml), and the reaction mixture was stirred at room temperature for 4 hours. The solid was filtered, washed with n-hexane (50 ml), and dried under high vacuum to give 1.69 g of (E)-N 2 -{[4-(methylsulfanyl)phenyl]methylidene}-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.47~1.50(m,2H), 1.62~1.69(m,1H), 1.84~1.89(m,1H), 3.07~3.10(m,2H), 3.20(s,3H), 3.67(t,J=6 .4Hz,1H), 7.28(d,J=8.4Hz,2H), 7.45(brs,2H), 7.64(d,J=8.4Hz,2H), 8.01(brs,2H), 8.19(s,1H), 9.55(s,1H);ESI-MS:m / z 313.10(M+H) + .

[0113] Example 20: (E)-N 2 Preparation of -{[2-hydroxy-3-methoxy-5-(prop-2-en-1-yl)phenyl]methylidene}-L-arginine [ka] L-arginine (0.86 g) was added to a solution of 2-hydroxy-3-methoxy-5-(prop-2-en-yl)benzaldehyde (1.0 g) in ethanol (25 ml), and the reaction mixture was stirred at room temperature for 16 hours. The solid was filtered, washed with n-hexane (20 ml), and dried under high vacuum to give 1.35 g of (E)-N 2 -{[2-hydroxy-3-methoxy-5-(prop-2-en-1-yl)phenyl]methylidene}-L-arginine was obtained as a solid. 1H NMR(400MHz,DMSO-d6)δ1.47~1.50(m,2H), 1.70~1.90(m,2H), 3.10~3.19( m,2H), 3.24(d,J=6.4Hz,1H), 3.42~3.45(m,1H), 3.73(s,3H), 3.81(t,J=5 .6Hz,1H), 5.08~5.08(m,2H), 5.89~5.99(m,1H), 6.88(s,1H), 6.72(s,1H) , 7.53(brs,4H), 8.30(s,1H), 9.49(brs,1H), 14.14(brs,1H);ESI-MS:m / z 349.20(M+H) + .

[0114] Example 21: (E)-N 2 Preparation of -{[2,3-dimethoxy-5-(prop-2-en-1-yl)phenyl]methylidene}-L-arginine> [ka] L-Arginine (0.81 g) was added to a solution of 2,3-dimethoxy-5-(prop-2-en-yl)benzaldehyde (1.0 g) in ethanol (20 ml), and the reaction mixture was stirred at room temperature for 4 hours. The solid was filtered, washed with n-hexane (50 ml), and dried under high vacuum to give 1.18 g of (E)-N 2 -{[2,3-Dimethoxy-5-(prop-2-en-1-yl)phenyl]methylidene}-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.45~1.50(m,2H), 1.59~1.64(m,1H), 1.88~1.91(m,1 H), 3.02~3.14(m,2H), 3.38(d,J=6.8Hz,2H), 3.68(t,J=6.8Hz,1H), 3.73(s,3 H), 3.81(s,3H), 5.03~5.13(m,2H), 5.89~5.99(m,1H), 6.93(d,J=2.0Hz,1H), 7.24(d,J=2.0Hz,1H), 7.75(brs,4H), 8.45(s,1H), 9.57(brs,1H);ESI-MS:m / z 363.20(M+H) + .

[0115] Example 22: Preparation of (E)-N2-{[2-hydroxy-3-(prop-2-en-1-yl)phenyl]methylidene}-L-arginine [ka] L-arginine (1.03 g) was added to a solution of 2-hydroxy-3-(prop-2-en-1-yl)benzaldehyde (1.0 g) in ethanol (10 ml), and the reaction mixture was stirred at room temperature for 16 hours. The solid was filtered, washed with n-hexane (25 ml), and dried under high vacuum to give 1.64 g of (£)-N2-{[2-hydroxy-3-(prop-2-en-1-yl)phenyl]methylidene}-L-arginine as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.48~1.53(m,2H), 1.72~1.77(m,1H), 1.90~1.95(m,1H) ), 3.09~3.18(m,2H), 3.26~3.37(m,2H), 3.81(t,J=5.6Hz,1H), 4.99~5.08(m,2 H), 5.92~6.02(m,1H), 6.69(t,J=7.6Hz,1H), 7.14(d,J=0.8Hz,1H), 7.20(d,J= 0.8Hz,1H), 7.42(brs,4H), 8.41(s,1H), 9.54(s,1H), 14.62(s,1H);ESI-MS:m / z 319.5(M+H) + .

[0116] Example 23: (E)-N 2 Preparation of -[(1H-indol-3-yl)methylidene]-L-arginine [ka] Indole-3-carboxaldehyde (1.76 g) was added to a slurry of L-arginine (1.11 g) in ethanol (30 ml), which was stirred at room temperature for 16 hours. The solid was filtered, washed with n-hexane, and dried under high vacuum to give 1.68 g of (E)-N 2-[(1H-indol-3-yl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.51~1.60(m,2H), 1.63~1.70(m,1H), 1.88~1.93(m,1H), 3.09~3.16(m,2H) , 3.61(t,J=6.4Hz,1H), 7.06(t,J=7.2Hz,1H), 7.15(t,J=7.2Hz,1H), 7.38(d,J=8.0Hz,1H), 7.52(br s.2H), 7.71(s,1H), 8.01(brs,2H), 8.25(d,J=8.0Hz,1H), 8.39(s,1H), 9.53(brs,1H), 11.46(brs,1H);ESI-MS:m / z 302.10(M+H)+.

[0117] Example 24: (E)-N 2 Preparation of -[(2H-1,3-benzodioxol-5-yl)methylidene]-L-arginine [ka] Piperonal (1 g) was added to a slurry of L-arginine (1.11 g) in ethanol (30 ml), and the mixture was stirred at room temperature for 16 hours. n-Hexane (30 ml) was added to the reaction mixture, which was stirred for an additional hour. The solid was filtered, washed with n-hexane, and dried under high vacuum to give 0.91 g of (E)-N 2 -[(2H-1,3-benzodioxol-5-yl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.40~1.54(m,2H), 1.61~1.66(m,1H), 1.85~1.87(m,1H), 3.07~3.09(m 2H), 3.64(t,J=6.4Hz,1H), 6.06(d,J=4.4Hz,2H), 6.95(d,J=8.0Hz,1H), 7.15(d,J=11.2Hz ,1H), 7.32(s,1H), 7.49(brs,2H), 7.56(brs,2H), 8.13(s,1H), 9.52(brs,1H);ESI-MS:m / z 307.30(M+H) + .

[0118] Example 25: (E)-N 2 Preparation of -[(furan-2-yl)methylidene]-L-arginine [ka] Furfural (1.56 g) was added to a slurry of L-arginine (2 g) in ethanol (50 ml), which was stirred for 18 hours at room temperature under a nitrogen atmosphere. The solvent was removed under vacuum, and n-hexane (20 ml) was added to the residue, which was stirred for 1 hour. The resulting solid was filtered, washed with n-hexane (10 ml), and dried under high vacuum to give 1.91 g of (E)-N 2 -[(furan-2-yl)methylidene]-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.45~1.50(m,2H), 1.60~1.67(m,1H), 1.82~1.85(m,1H), 3.07~3.09(m,2H), 3.63(t,J=6.80Hz,1H), 6.58 ~6.9(m,1H), 6.86(d,J=3.2Hz,1H), 7.45(brs,2H), 7.55(d,J=1.2Hz,1H), 8.06(brs,2H), 8.10(s,1H), 9.45(brs,1H);ESI-MS:m / z 253.20(M+H) + .

[0119] Example 26: (E)-N 2 Preparation of -[(5-methylfuran-2-yl)methylidene]-L-arginine [ka] L-arginine (1.5 g) was added to a solution of 5-methylfurfural (1.0 g) in ethanol (20 ml). The reaction mixture was stirred at room temperature for 16 hours. The solid was filtered, washed with ethanol (10 ml), and dried under high vacuum to give 1.99 g of (E)-N 2 -[(5-methylfuran-2-yl)methylidene]-L-arginine was obtained as a solid. 1H NMR (400MHz, DMSO-d6) δ1.45~1.85(m,4H), 2.31(s,3H), 3.06~3.10(m,2H), 3.57(t,J=6.4Hz) ,1H), 6.22(d,J=2.8Hz,1H), 6.71(d,J=2.8Hz,1H), 7.50(brs,5H), 7.99(s,1H);ESI-MS:m / z 267.20(M) + .

[0120] Example 27: (E)-N 2 Preparation of -{[5-(hydroxymethyl)furan-2-yl]methylidene}-L-arginine [ka] L-arginine (1.32 g) was added to a solution of 5-(hydroxymethyl)furan-2-carbaldehyde (1.0 g) in ethanol (25 ml). The reaction mixture was stirred at room temperature for 16 hours. The solid was filtered, washed with ethanol (10 ml) and n-hexane (25 ml), and then dried under high vacuum to give 1.71 g of (E)-N 2 -{[5-(hydroxymethyl)furan-2-yl]methylidene}-L-arginine was obtained as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.40~1.55(m,2H), 1.60~1.67(m,1H), 1.81~1.90(m,1H), 3.04~3.12(m,2H), 3.61(t,J=6.4Hz,1H), 4.4 2(s,2H), 5.50(brs,1H), 6.39(d,J=2.8Hz,1H), 6.77(d,J=2.4Hz,1H), 7.48(brs,4H), 8.09(s,1H), 9.50(brs,1H);ESI-MS:m / z 283.20(M) + .

[0121] Example 28: Preparation of (E)-N2-[(naphthalen-1-yl)methylidene]-L-arginine [ka] L-arginine (0.96 g) was added to a solution of 1-naphthaldehyde (1 g) in ethanol (15 ml) at room temperature. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. The solid product was filtered, washed with cold ethanol (10 ml) followed by n-hexane (40 ml), and then dried under high vacuum to obtain 1.19 g of (E)-N2-[(naphthalen-1-yl)methylidene]-L-arginine as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.56(br s,2H), 1.74~1.81(m,1H), 1.97~2.05(m,1H), 3.13~3.14(m,2H), 3.82(t,J=6.4Hz,1H), 7.34(br s,4H), 7.55~7.63(m,3H), 7.88(d,J=6.8Hz,1H), 7.99(t,J=7.2Hz,2H)8.86(s,1H), 9.17(d,J=8.4Hz,1H), 9.79(br s,1H);ESI-MS:m / z 313.12(M+H) + .

[0122] Example 29: Preparation of (E)-N2-[(pyridin-3-yl)methylidene]-L-arginine [ka] L-arginine (0.9 g) was added to a solution of nicotinaldehyde (1 g) in ethanol (10 ml) at room temperature. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. The solid product was filtered, washed with cold ethanol (10 ml) followed by n-hexane (30 ml), and then dried under high vacuum to obtain 0.91 g of (E)-N2-[(pyridin-3-yl)methylidene]-L-arginine as a solid. 1H NMR(400MHz,DMSO-d6)δ1.46~1.52(m,2H), 1.68~1.73(m,1H), 1.90~1.93(m,1H), 3.09(br s,1H), 3.74(t,J=6.4Hz,1H), 7.29(br s,5H), 7.45(dd,J=5.0Hz,7.8Hz,1H), 8.11(d,J=8.0Hz,1H), 8.33(s,1H), 8.61(dd,J=1.6Hz,4.8Hz,1H), 8.86(s,1H), 9.71(br s,1H);ESI-MS:m / z 264.20(M+H) + .

[0123] Example 30: Preparation of (E)-N2-[(naphthalen-2-yl)methylidene]-L-arginine [ka] L-arginine (0.90 g) was added to a solution of 2-naphthaldehyde (1 g) in ethanol (10 ml) at room temperature. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. The solid product was filtered, washed with cold ethanol (10 ml) followed by n-hexane (40 ml), and then dried under high vacuum to obtain 1.13 g of (E)-N2-[(naphthalen-2-yl)methylidene]-L-arginine as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.49~1.556(m,2H), 1.71~1.76(m,1H), 1.94~1.97(m,1H), 3.11(br s,2H), 3.78(t,J=6.4Hz,1H), 7.32(br s,4H), 7.54~7.58(m,2H), 7.92~7.96(m,3H), 7.98~8.01(m,1H)8.17(s,1H), 8.42(s,1H), 9.80(br s,1H);ESI-MS:m / z 313.28(M+H) + .

[0124] Example 31: Preparation of (E)-N2-[(thiophen-3-yl)methylidene]-L-arginine [ka] L-arginine (0.9 g) was added to a solution of thiophene-3-carbaldehyde (1 g) in ethanol (10 ml) at room temperature. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. The solid product was filtered, washed with cold ethanol (10 ml) followed by n-hexane (20 ml), and then dried under high vacuum to give 0.48 g of (E)-N2-[(thiophen-3-yl)methylidene]-L-arginine as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.47(br s,2H), 1.61-1.66(m,1H), 1.84~1.88(m,1H), 3.06~3.09(m,2H), 3.62(t,J=6.4Hz,1H), 7.33~7.60(br s,4H), 7.43(d,J=4.4Hz,1H), 7.55~7.56(m,1H), 7.87(s,1H)8.25(s,1H), 9.69(br s,1H);ESI-MS:m / z 269.40(M+H) + .

[0125] Example 32: Preparation of (E)-N2-{[2-methoxy-3-(prop-2-en-1-yl)phenyl]methylidene}-L-arginine [ka] L-arginine (1.89 g) was added to a solution of 2-methoxy-3-(prop-2-en-1-yl)benzaldehyde (2 g) in isopropyl alcohol (20 ml) at room temperature. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. The solid product was filtered, washed with n-hexane (20 ml), and then dried under high vacuum to obtain 2.34 g of (E)-N2-{[2-methoxy-3-(prop-2-en-1-1)phenyl]methylidene}-L-arginine as a solid. 1H NMR(400MHz,DMSO-d6)δ1.50(br s,2H), 1.66~1.71(m,1H), 1.88~1.92(m,1H), 3.09(d,J=6.4Hz,2H)3.40(d,J=6.4Hz,2H), 3.72(s,3H), 3.74~ 3.76(m,1H), 5.05~509(m,2H), 5.93~6.01(m,1H), 7.12(t,J=7.6Hz,1H), 7.26(d,J=7.6Hz,1H), 7.31~7.36(br s,4H), 7.73(d,J=8.0Hz,1H), 8.48(s,1H), 9.70(br s, 1H); ESI-MS: m / z 333.20 (M+H) + .

[0126] Example 33: Preparation of (E)-N2-[(7-methoxy-2H-1,3-benzodioxol-5-yl)methylidene]-L-arginine [ka] L-arginine (0.96 g) was added to a solution of 7-methoxy-2H-1,3-benzodioxole-5-carbaldehyde (1 g) in ethanol (20 ml) at room temperature. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. The solid product was filtered, washed with n-hexane (20 ml), and then dried under high vacuum to obtain 1.23 g of (£)-N2-[(7-methoxy-2H-1,3-benzodioxole-5-yl)methylidene]-L-arginine as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.46(br s,2H), 1.63~1.65(m,1H), 1.87~1.88(m,1H), 3.05~3.37(m,2H), 3.65(t,J =6.6Hz,1H), 3.85(s,3H), 6.05(s,2H), 6.95(s,1H), 7.04(s,1H), 7.46(br s,3H), 7.99(br s,1H), 8.12(s,1H), 9.48(br s,1H);ESI-MS:m / z 337.20(M+H) + .

[0127] Example 34: Preparation of (E)-N2-[(2H-1,3-benzodioxol-4-yl)methylidene]-L-arginine [ka] L-arginine (1.11 g) was added to a solution of 2H-1,3-benzodioxole-4-carbaldehyde in ethanol (20 ml) at room temperature. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. The solid product was filtered, washed with n-hexane (20 ml), and then dried under high vacuum to obtain 1.41 g of (E)-N2-[(2H-1,3-benzodioxole-4-yl)methylidene]-L-arginine as a solid. 1 H NMR(400MHz,DMSO-d6)δ1.47(br s,2H), 1.63~1.72(m,1H), 1.84~1.89(m,1H), 3.07~3.09(m,2H), 3.69(t,J=6.4Hz,1H), 6.0 9(s,2H), 6.85(t,J=7.6Hz,1H), 6.95(d,J=8.0Hz,1H), 7.26(d,J=7.6Hz,1H), 7.52~7.91(br s,5H), 8.32(s,1H), 9.36(br s,1H);ESI-MS:m / z 307.20(M+H) + .

[0128] Example 35: Stability study of compounds of the present invention The compounds of the present invention were stored under the conditions [room temperature and accelerated storage conditions (ATS)] as shown in the table below, and purity was estimated by HPLC. Properly packaged material was subjected to the conditions mentioned in the table below.

[0129] [Table 1]

[0130] The following examples illustrate the basic methodology and versatility of the compositions of the present invention. It should be noted that the present invention is not limited to these examples. The composition form, excipients, and concentrations of active substances and excipients can be replaced with any other form, excipient, and concentration as described in the present invention.

[0131] Example 36: General procedure for preparation of water-disintegrating granules (GR) The compound of the present invention is crushed in a jet mill to the desired particle size of less than 50 microns, then all the raw materials are added and mixed in a ribbon blender to obtain a homogeneous powder.The required amount of water is added to the above mixture to prepare a dough, and then the material is granulated in a suitable equipment and dried to obtain granules.

[0132] The following water-disintegrable granular (GR) composition was prepared as in Example 36.

[0133] [Table 2]

[0134] Example 37: General procedure for preparation of extruded granules (WG) The compound of the present invention is mixed with dispersing agent, wetting agent and inert excipient in a ribbon blender, and then crushed to a desired particle size in a jet mill.The required amount of water is added to the above mixture to prepare a dough, and then the material is granulated in a suitable equipment and dried to obtain granules.

[0135] The following extruded granular (WG) compositions were prepared as in Example 37.

[0136] [Table 3]

[0137] Example 38: General procedure for preparation of spray-dried granules (WG) The compound of the present invention is mixed with all the raw materials in 100 parts of water and milled to the desired particle size. The milled slurry is then spray dried / fluid bed dried to obtain granules.

[0138] The following spray dried granular (WG) composition was prepared as in Example 38.

[0139] [Table 4]

[0140] Example 39: General procedure for the preparation of WP The compound of the present invention is blended in a ribbon blender with the required amount of dispersant, wetting agent, and inert ingredients. The blended material is passed through a jet mill to reduce the particle size and blended for an additional hour to obtain a product of the desired composition.

[0141] The following wettable powder (WP) compositions were prepared as in Example 39.

[0142] [Table 5]

[0143] Example 40: General procedure for preparation of suspension concentrate (SC) The required amount of surfactant and antifreeze agent are mixed with the defined amount of water.The compound of the present invention is further added to the homogenized mixture, and the whole mixture is continuously stirred for about 20 minutes until it becomes homogenous.Half the amount of antifoaming agent is added while being continuously homogenized to obtain a liquid suspension.Then, the obtained suspension is passed through a wet grinder to reduce particle size.The required amount of thickener, preservative and the remaining water and antifoaming agent are added to obtain the product of desired composition.

[0144] Example 41: General procedure for the preparation of coated granules (GR) The required amounts of stabilizers, surfactants, colorants, and binders are mixed and heated to the desired temperature in a drum coater. The required amount of river sand is added to the drum coater and mixed. The compound of the present invention with the desired particle size is added to a ribbon blender and mixed to obtain a product with the desired composition.

[0145] Example 42: General procedure for preparation of dry seed treatment powder (DS) The compound of the present invention is blended in a ribbon blender with the required amount of pigment, wetting agent, and inert ingredients. The blended material is passed through a jet mill to reduce particle size and blended for an additional hour to obtain a product of the desired composition.

[0146] Example 43: General procedure for preparation of water-dispersible powder (WS) for slurry processing The compound of the present invention is blended in a ribbon blender with the required amount of pigment, dispersant, wetting agent, and inert ingredients. The blended material is passed through a jet mill to reduce the particle size and blended for an additional hour to obtain a product of the desired composition.

[0147] The following suspension concentrate (SC), coated granule (GR), powder for dry seed treatment (DS) and water dispersible powder for slurry treatment (WS) compositions were prepared as in Examples 40, 41, 42 and 43, respectively.

[0148] [Table 6]

[0149] Example 43: Determination of nematicidal activity against root-knot nematodes (Meloidogyne species) Test compound (4 mg) was dissolved in 40 μl of DMSO to prepare a 100,000 ppm stock solution. A clear solution was obtained by vortexing. A nematode suspension (250 μl) containing 70–100 juveniles (J2) of the root-knot nematode Meloidogyne species was pipetted into each well of a 24-well bioassay plate. Sterile water (1 ml) was pipetted into an unused 2.5 ml Eppendorf microcentrifuge tube. The desired concentration (500 ppm) of compound was prepared by adding the stock solution to the 2.5 ml Eppendorf microcentrifuge tube. Four replicates were maintained for each treatment. Bioassay plates were incubated in a humidity chamber at 22 ± 2°C and 70 ± 5% RH. Dead / inactive nematodes were counted under a microscope at 24, 48, 72, and 96 hours after incubation, and percent mortality was calculated.

[0150] [Table 7]

[0151] [Table 8]

Claims

1. Compounds of formula (I) 【Chemistry 1】 (I) wherein 【Chemistry 2】 but, 【Transformation 3】 or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein:

2. 2. The compound of claim 1 , 【Chemistry 4】 but, 【Transformation 5】 A compound characterized in that:

3. 2. The compound of claim 1 , 【Transformation 6】 but, 【Transformation 7】 A compound characterized in that:

4. 10. The compound of claim 1, wherein the compound is 【Transformation 8】 or an agrochemically acceptable salt or N-oxide thereof, wherein the compound is selected from the group consisting of:

5. 10. The compound of claim 1, having the formula 【Chemistry 9】 or an agriculturally acceptable salt or N-oxide thereof.

6. 10. The compound of claim 1, having the formula 【Chemistry 10】 or an agriculturally acceptable salt or N-oxide thereof.

7. 10. The compound of claim 1, having the formula 【Chemistry 11】 or an agriculturally acceptable salt or N-oxide thereof.

8. 10. The compound of claim 1, having the formula 【Chemistry 12】 or an agriculturally acceptable salt or N-oxide thereof.

9. Compounds of formula (I) 【Chemistry 13】 (I) or a pesticidally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, and at least one pesticidally acceptable excipient, During the ceremony, 【Chemistry 14】 but, 【Chemistry 15】 An agricultural composition characterized by:

10. 10. The agricultural composition of claim 9, wherein the pesticidally acceptable excipient is selected from one or more of surfactants, disintegrants, fillers or carriers or diluents, spreading agents, colorants, anti-caking agents, binders, buffers or pH adjusters or neutralizing agents, pigments, stabilizers, anti-foaming or defoaming agents, penetrating agents, structuring agents, humectants, sticking agents, anti-freeze or freezing point depressants, chelating or complexing or sequestering agents, and preservatives.

11. formula 【Chemistry 16】 or an agriculturally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

12. formula 【Chemistry 17】 or an agriculturally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

13. formula [Chemistry 18] or an agriculturally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

14. formula 【Chemistry 19】 or an agriculturally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

15. formula 【Chemistry 20】 or an agriculturally acceptable salt or N-oxide thereof, and at least one agriculturally acceptable excipient.

16. 16. An agricultural composition according to any one of claims 9 to 15, characterized in that the composition is in the form of a solid or liquid or gel or paste.

17. 17. The agricultural composition according to claim 16, wherein the solid composition is in the form of spherical granules, extruded granules, water-disintegrating granules, wettable powder, water-dispersible granules, dustable powder, powder for dry seed treatment, water-disintegrating tablet or water-dispersible powder for slurry seed treatment.

18. 17. The agricultural composition according to claim 16, wherein the liquid composition is in the form of a liquid suspension or suspension concentrate, a suspoemulsion, an oil dispersion, a flowable concentrate, or a suspension concentrate for seed treatment, in a trace amount.

19. A method for treating or controlling parasitic nematodes or nematode infections in plants comprising administering to a plant a compound of formula (I) 【Chemistry 21】 (I) or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: 【Chemistry 22】 teeth, 【Chemistry 23】 is] 20. A method comprising administering

20. 1. A method for treating or controlling parasitic nematodes or nematode infections in plants, comprising the step of: 【Chemistry 24】 or a pesticidally acceptable salt or N-oxide thereof.

21. 1. A method for treating or controlling parasitic nematodes or nematode infections in plants, comprising the step of: 【Chemistry 25】 or a pesticidally acceptable salt or N-oxide thereof.

22. A process for the preparation of a compound of formula (I), comprising combining a compound of formula (A) with a compound of formula (B) 【Chemistry 26】 [In the formula, 【Chemistry 27】 teeth, 【Chemistry 28】 is] A process comprising:

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