HK1238637B - 5-fluoro-4-imino-3-(substituted)-3,4-dihydropyrimidin-2-(1h)-one derivatives - Google Patents

Description

5-Fluoro-4-imino-3-(substituted)-3,4-dihydropyrimidin-2(1H)one derivatives

This application is a divisional application of a patent application filed on August 15, 2012, with application number 201280049656.1 (international application number PCT/US2012/050930), and with the invention name “5-Fluoro-4-imino-3-(substituted)-3,4-dihydropyrimidin-2(1H)one derivatives”.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent Application No. 61/524,506, filed August 17, 2011, which is expressly incorporated herein by reference.

Background Technology and Brief Description of the Invention

Fungicides, of natural or synthetic origin, are compounds used to protect and/or cure plants from damage caused by agriculturally relevant fungi. Generally speaking, no single fungicide is effective in all situations. Therefore, research is underway to develop fungicides with improved performance, greater ease of use, and lower cost.

The present disclosure relates to 3-alkyl-5-fluoro-4-imino-3,4-dihydropyrimidin-2(1H)one compounds and their use as fungicides. The compounds of the present disclosure can provide protection against ascomycetes, basidiomycetes, deuteromycetes, and oomycetes.

One embodiment of the present invention may include a compound of formula I:

Where ^R1 is:

C ₁ -C ₆ alkyl optionally substituted with 1-3 R ³ ;

C ₁ -C ₆ alkenyl optionally substituted with 1-3 R ³ ;

C ₃ -C ₆ alkynyl optionally substituted with 1 to 3 R ³ ;

phenyl or benzyl, wherein each of the phenyl or benzyl groups may be optionally substituted with 1-3 R ⁴ , or substituted with a 5- or 6-membered saturated or unsaturated ring system, or substituted with a 5-6 fused ring system, or substituted with a 6-6 fused ring system, each containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ ,

-(CHR ⁵ ) _m OR ⁶ ;

-C(=O)R ⁷ ;

-C(＝S)R ⁷ ;

-C(=O)OR ⁷ ;

-C(＝S)OR ⁷ ;

-S(O) ₂ R ⁷ ;

-(CHR ⁵ ) _m N(R ⁸ )R ⁹ ;

-C(=O)N(R ⁸ )R ⁹ ; or

-C(=S)N(R ⁸ )R ⁹ ;

Where m is an integer from 1 to 3;

^R2 is:

H; or

C ₁ -C ₆ alkyl optionally substituted with R ³ ;

R ³ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, amino, halothio, C ₁ -C ₃ alkylamino, _{C 2} -C ₆ alkoxycarbonyl, C 2 -C _{6 alkylcarbonyl, C 2 -C 6} alkylaminocarbonyl, hydroxy, C ₃ -C ₆ trialkylsilyl, or substituted with a 5- or 6-membered saturated or unsaturated ring system, or substituted with a 5-6 fused ring system, or substituted with a 6-6 fused ring system, each ring system containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ ;

R ⁴ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, halothio, amino, C ₁ -C ₆ alkylamino, C ₂ -C ₆ dialkylamino, C ₂ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylsulfonyl or C ₂ -C ₆ alkylcarbonyl, nitro, hydroxy, or cyano;

R ⁵ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl or benzyl, wherein each of said phenyl or benzyl groups may be optionally substituted with 1 to 3 R ⁴ ;

R ⁶ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, phenyl or benzyl (wherein each of the phenyl or benzyl groups may be optionally substituted with 1-3 R ⁴ , or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system, each containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ ), biphenyl or naphthyl optionally substituted with 1-3 R ⁴ ;

R ⁷ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, phenyl or benzyl (wherein each of the phenyl or benzyl groups may be optionally substituted with 1-3 R ⁴ , or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system, each containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ ), biphenyl or naphthyl optionally substituted with 1-3 R ⁴ ;

R ⁸ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, phenyl or benzyl (wherein each of the phenyl or benzyl groups may be optionally substituted with 1-3 R ⁴ , or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system, each containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ ), biphenyl or naphthyl optionally substituted with 1-3 R ⁴ ; and

R ⁹ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, or benzyl, wherein the benzyl group may be optionally substituted with 1 to 3 R ⁴ ;

Alternatively, R ⁸ and R ⁹ may together form a 5- or 6-membered saturated or unsaturated ring containing 1 to 3 heteroatoms, wherein each ring may be optionally substituted with 1 to 3 R ⁴ .

Another embodiment of the present invention may include a fungicidal composition for controlling or preventing fungal attack, the composition comprising a compound as described below and a phytologically acceptable carrier material.

Another embodiment of the present invention may include a method for controlling or preventing fungal attack on plants, comprising the steps of applying a fungicidally effective amount of one or more compounds as described below to at least one of the following loci: the fungus, the plant, an area adjacent to the plant, and seeds suitable for producing the plant.

The term "alkyl" refers to branched, unbranched or cyclic carbon chains and includes methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The term "alkenyl" refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds, including ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclohexenyl and the like.

The term "alkynyl" refers to a branched or unbranched carbon chain containing one or more triple bonds and includes propynyl, butynyl, and the like.

Unless otherwise stated, the term 'R' as used throughout this specification refers to a group C _2-8 alkyl, C _3-8 alkenyl or C _3-8 alkynyl.

The term "alkoxy" refers to an -OR substituent.

The term "alkoxycarbonyl" refers to a -C(O)-OR substituent.

The term "alkylcarbonyl" refers to a -C(O)-R substituent.

The term "alkylsulfonyl" refers to a _-SO2 -R substituent.

The term "alkylthio" refers to an -S-R substituent.

The term "halothio" refers to a sulfur substituted with three or five F substituents.

The term "haloalkylthio" refers to an alkylthio group substituted with Cl, F, I or Br or any combination thereof.

The term "alkylaminocarbonyl" refers to a -C(O)-N(H)-R substituent.

The term "trialkylsilyl" refers to _-SiR3 .

The term "cyano" refers to a -C≡N substituent.

The term "hydroxy" refers to an -OH substituent.

The term "amino" refers to a _-NH2 substituent.

The term "alkylamino" refers to an -N(H)-R substituent.

The term "dialkylamino" refers to a _-NR2 substituent.

The term "alkoxyalkyl" refers to an alkoxy substituent on an alkyl group.

The term "halogen" or "halo" refers to one or more halogen atoms, which are defined as F, Cl, Br and I.

The term "nitro" refers to a _-NO2 substituent.

Throughout this invention, references to compounds of Formula I also include optical isomers and salts thereof and hydrates thereof. Specifically, when Formula I contains a branched alkyl group, it is understood that the compound includes optical isomers and racemates thereof. Examples of salts include hydrochlorides, hydrobromides, hydroiodides, and the like. In addition, compounds of Formula I may include tautomeric forms.

Some of the compounds disclosed in this application may exist as one or more isomers. It will be appreciated by those skilled in the art that one isomer may be more active than another. For clarity, the structures disclosed herein are drawn in only one geometric form, but are intended to represent all geometric forms and tautomeric forms of the molecules.

It will also be understood by those skilled in the art that, unless otherwise indicated, additional substitutions are permissible as long as chemical bonding and strain energy rules are met and the product still exhibits fungicidal activity.

Another embodiment of the present invention is the use of a compound of formula I for protecting plants from attack by phytopathogenic microorganisms or for treating plants attacked by phytopathogenic microorganisms, which comprises applying a compound of formula I or a composition containing said compound to the soil, plants, plant parts, leaves and/or seeds.

Furthermore, another embodiment of the present invention is a composition for protecting plants from attack by phytopathogenic microorganisms and/or treating plants attacked by phytopathogenic microorganisms, said composition comprising a compound of formula I and a phytologically acceptable carrier substance.

Other features and advantages of the present invention will become apparent to those skilled in the art upon consideration of the following detailed description of exemplary embodiments, which illustrates the best mode of carrying out the invention presently understood.

Detailed description of the present invention

The compounds of this invention can be applied as a compound or as a preparation containing the compound by any of various known techniques. For example, the compound can be applied to the roots, seeds or leaves of plants to prevent and treat various fungi without destroying the commercial value of the plants. The substance can be applied in the form of any commonly used formulation type, for example as a solution, dust, wettable powder, flowable concentrate or emulsifiable concentrate.

Preferably, the compounds of the present invention are applied in the form of a formulation comprising one or more compounds of Formula I and a botanically acceptable carrier. Concentrated formulations can be dispersed in water or other liquids for application, or the formulation can be a dust or granules, which can be applied immediately without further treatment. The formulations can be prepared according to methods common in the field of agricultural chemistry.

The present invention contemplates the use of all vehicles by which the one or more compounds may be formulated for delivery and use as fungicides. Typically, the formulations are administered as aqueous suspensions or emulsions. The suspensions or emulsions may be prepared from water-soluble, water-suspendable, or emulsifiable formulations, which are generally referred to as wettable powders when they are solids, or as emulsifiable concentrates, aqueous suspensions, or suspension concentrates when they are liquids. It will be readily appreciated that any substance to which these compounds may be added may be used, provided that it produces the desired effect without significantly hindering the activity of these compounds as antifungal agents.

Wettable powders that can be compressed into water-dispersible granules comprise an intimate mixture of one or more compounds of Formula I, an inert carrier, and a surfactant. The concentration of the compound in the wettable powder can range from about 10% to about 90% by weight, more preferably from about 25% to about 75% by weight, based on the total weight of the wettable powder. In preparing wettable powder formulations, the compound can be mixed with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clay, diatomaceous earth, purified silicates, and the like. In such operations, the finely divided carrier and surfactant are typically blended and ground with the compound.

The emulsifiable concentrate of formula I compound can be included in the compound of conventional concentration in suitable liquid, for example from about 10wt% to about 50wt%, in the gross weight of the concentrate. The compound can be dissolved in an inert carrier and an emulsifier, and the inert carrier is a mixture of a water-miscible solvent or a water-immiscible organic solvent. The concentrate can be diluted with water and oil to form a spray mixture in the form of an oil-in-water emulsion. Useful organic solvents include aromatic moieties, particularly high-boiling naphthalene moieties and olefinic moieties such as heavy aromatic naphthalene oils, of petroleum. Other organic solvents such as terpene solvents can also be used, including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol.

The emulsifier that can be advantageously adopted by the present invention can be easily determined by those skilled in the art and includes various nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers and amphoteric emulsifiers, or a blend of two or more emulsifiers. The example of the nonionic emulsifier used in the preparation of the emulsifiable concentrate includes polyalkylene glycol ethers, and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxide, for example ethoxylated alkylphenols and carboxylic acid esters dissolved with polyols or polyoxyalkylenes. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include oil-soluble salts (for example, calcium salts), oil-soluble salts or suitable salts of sulfated polyglycol ethers and phosphated polyglycol ethers of alkylaryl sulfonic acids.

Representative organic liquids that can be used in the preparation of emulsifiable concentrates of the compounds of the present invention are aromatic liquids such as xylene and propylbenzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkylamides of various fatty acids, in particular dimethylamides and glycol derivatives of fatty glycols such as n-butyl ether, ethyl ether or methyl ether of diethylene glycol, methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffin oil, etc.; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc.; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids can also be used in the preparation of emulsifiable concentrates. Organic liquids include xylene and propylbenzene fractions, with xylene being most preferred in some cases. In liquid formulations, a surface active dispersant is typically used in an amount of 0.1 to 20 wt % based on the total weight of the dispersant and the one or more compounds. The formulation may also contain other compatible additives, such as plant growth regulators and other biologically active compounds used in agriculture.

Aqueous suspension comprises that one or more water-insoluble compounds of formula I are dispersed in the suspension in aqueous vehicle, and in the gross weight of aqueous suspension, concentration is about 5wt%-about 50wt%.Prepare suspension as follows: fine grinding one or more described compounds, the compound through grinding is violently mixed in vehicle, and described vehicle is made up of water and the surfactant selected from above-mentioned same type.Also can add other ingredients, for example inorganic salt and synthetic glue or natural rubber, to increase density and viscosity of aqueous vehicle.Usually the most effective is to grind and mix simultaneously in the following manner: prepare aqueous mixture and homogenize in equipment for example sand mill, ball mill or piston homogenizer.

Aqueous emulsions comprise an emulsion of one or more water-insoluble insecticidal active ingredients emulsified in an aqueous vehicle, typically at a concentration ranging from about 5% to about 50% by weight, based on the total weight of the aqueous emulsion. If the insecticidal active ingredient is a solid, it must be dissolved in a suitable water-immiscible solvent prior to preparing the aqueous emulsion. Emulsions are prepared by emulsifying the liquid insecticidal active ingredient or a water-immiscible solution thereof in an aqueous medium, typically containing a surfactant that aids in the formation and stabilization of the emulsion. This is typically accomplished with the aid of vigorous agitation provided by a high-shear mixer or homogenizer.

Formula I compound can also be used as the form of granular preparation, and described granular preparation can be particularly used for being applied to soil.Based on the gross weight of granular preparation, described granular preparation generally contains about 0.5wt%-about 10wt% described compound dispersed in inert carrier, and described inert carrier is made up of roughly crushed inert material completely or mostly, and described inert material is for example attapulgite, bentonite, diatomaceous earth, clay or similar cheap material.Described preparation is generally prepared as follows: described compound is dissolved in suitable solvent, and it is applied to granular carrier, and described granular carrier has been pre-made into suitable particle size (scope is about 0.5 to 3mm).Suitable solvent is the solvent that described compound can be substantially or completely dissolved therein.Described preparation also can be prepared as follows: described carrier and compound and solvent are made into paste or paste, then crushed and dried to obtain required particle size.

Dusts containing a compound of formula I can be prepared by thoroughly mixing one or more of the compounds in powder form with a suitable dusty agricultural carrier (e.g., kaolin clay, ground volcanic rock, etc.). The dust can suitably contain from about 1% to about 10% of the compound based on the total weight of the dust.

The formulation may additionally contain an adjuvant surfactant to enhance the deposition, wetting and penetration of the compound onto the target crops and microorganisms. These adjuvant surfactants may optionally be used as a component of the formulation or as a tank mix. The amount of the adjuvant surfactant is typically 0.01 to 1.0 volume %, preferably 0.05 to 0.5 volume %, based on the spray volume of water. Suitable adjuvant surfactants include, but are not limited to, ethoxylated nonylphenols, ethoxylated synthetic alcohols or ethoxylated natural alcohols, sulfosuccinates or sulfosuccinates, ethoxylated organosiloxanes, ethoxylated fatty amines, blends of surfactants with mineral oils or vegetable oils, crop oil concentrates (mineral oil (85%) + emulsifier (15%)); nonylphenol ethoxylates; benzyl coconut oil alkyl dimethyl quaternary ammonium salts; blends of petroleum hydrocarbons, alkyl esters, organic acids, and anionic surfactants; C ₉ -C ₁₁ alkyl polyglycosides; phosphated alcohol ethoxylates; natural primary alcohols (C ₁₂ -C ₁₆ ) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl endcap; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallowamine ethoxylate (15EO) and PEG (400) dioleate-99. The formulation may also include oil-in-water emulsions such as those disclosed in U.S. Patent Application No. 11/495,228, the disclosure of which is incorporated herein by reference.

The formulation may optionally include a combination containing other insecticidal compounds. This additional insecticidal compound can be a fungicide, insecticide, herbicide, nematocide, acaricide, arthropodicide, bactericide or a combination thereof, and the additional insecticidal compound is compatible with the compounds of this invention in the medium selected for application and does not antagonize the activity of the compounds of this invention. Therefore, in these embodiments, the other insecticidal compounds are used as supplementary toxicants for the same or different insecticidal purposes. The compound of formula I and the insecticidal compound in the combination can generally be present in a weight ratio of 1:100 to 100:1.

The compounds of the present invention can also be combined with other fungicides to form fungicidal mixtures and their synergistic mixtures. The fungicidal compounds of the present invention are usually applied together with one or more other fungicides to prevent and treat a wider range of undesirable diseases. When applied together with other fungicides, the compounds claimed in the present invention can be formulated with the one or more other fungicides, can be tank mixed with the one or more other fungicides, or can be applied sequentially with the one or more other fungicides. The other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces, quisqualis, azaconazole, azoxystrobin, Bacillus subtilis), benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminophene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux Mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide), captafol, captan, carbendazim, carboxin, carpropamid, carvone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium Minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylene bis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base freebase), edifenphos, enestrobin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, triphenyltin hydroxide hydroxide), ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl aluminum, fuberidazole, furaxyl, furametpyr, guazatine, guazatine acetate acetate), sodium tetrasulfide (GY-81), hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprethiolane, isopyrazam, isotianil, laminarin, kasugamycin, kasugamycin hydrochloride hydrate), kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric chloride, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl methacrylate isothiocyanate), metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acid), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate acetate), phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroquinoline sulfate sulfate), probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, and Reynoutria sachalinensis extract. extract), sedaxane, silthiofam, simeconazole, sodium 2-phenyl phenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z071, SYP-Z048, tar oil, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol ol), triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila), Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantean, Streptomyces griseoviridis, Trichoderma spp., (R,S)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate hydrate), l-chloro-2,4-dinitronaphthalene, l-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine-1,1,4,4-tetraoxide, 2-methoxyethyl mercury acetate, 2-methoxyethyl mercury chloride, 2-methoxyethyl mercury silicate silicate), 3-(4-chlorophenyl)-5-methyl rhodanine, 4-(2-nitroprop-l-enyl)phenyl thiocyanate, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril, benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate mercury sulfate), bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione one), ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944), hexylthiofos, procyclidine (ICIA0858), isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methyl mercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenyl-succinimide, N-3-nitrophenyl itaconimide, natamycin, N-ethyl mercurio-4-toluenesulfonylanilide sulfonanilide), nickel bis(dimethyl dithiocarbamate), octachloroketone (OCH), phenylmercury dimethyl dithiocarbamate, phenylmercury nitrate, phosdiphen, picolinamide UK-2A and its derivatives, prothiocarb, prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, 5-acetyl-8-hydroxyquinoline (quinacetol), quinacetol salt sulfate), quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid and zarilamid, and any combination thereof.

In addition, the compounds of the present invention can be combined with other pesticides, including insecticides, nematocides, acaricides, arthropodicides (arthropodicide), fungicides or their combinations, which are compatible with the compounds of the present invention in the medium selected for application and do not antagonize the activity of the compounds of the present invention to form pesticidal mixtures and their synergistic mixtures. The fungicidal compounds of the present invention are usually co-applied with one or more other pesticides to prevent and control a wider range of undesirable pests. When co-applied with other pesticides, the compounds claimed in the present invention can be formulated with other pesticides, can be mixed with other pesticide tanks or can be applied sequentially with other pesticides. Common insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, and amiton. oxalate), amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid acid), bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride tetrachloride), carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I), cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate oleate), coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cy thioate), DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methyl, diafenthiuron, dialifos, diatomaceous earth earth), diazinon, dicapthion, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, Dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, ammonium dinitrocresol, potassium dinitrocresol, sodium dinitrocresol, doramectin, ecdysterone, emamectin, emamectin benzoate benzoate), EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide oxide), etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, cypermethrin fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, flufiprole, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthie tan), furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide cyanide), hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III III), kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan, mercurous chloride chloride), mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, emthoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methyl chloroform chloroform), methylenechloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycinoxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, Monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, Oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate ( phorate), phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, arsenite), potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II II), pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate thiocyanate), sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfurylfluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebufenphos bupirimfos), teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate oxalate), thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, etherbenzenesulfonate [0014] The present invention further comprises the following: triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, and any combination thereof.

In addition, the compounds of the present invention can be combined with herbicides that are compatible with the compounds of the present invention and do not antagonize the activity of the compounds of the present invention in the medium selected for application to form insecticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present invention are generally co-applied with one or more herbicides to control a wider range of undesirable plants. When co-applied with herbicides, the compounds claimed herein can be formulated with the herbicide, can be tank-mixed with other herbicides, or can be applied sequentially with the herbicide. Common herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alcohol), alorac, amethidione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate sulfamate), anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor , benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid acid), cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlorfenac, chlorfenprop, chlorfenapyr ... hlornitrofen), chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate sulfate), CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dichlorvos, mba), dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimeth enamid), dimethenamid-P, dimexano, dimidazon, diinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, 2,4-D, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalflu ralin), ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate sulfate), flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flupyridazine flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupro pacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate inate-P), glyphosate, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapic yr), imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozine in), isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron , methylarsonic acid (MAA), monoammonium methylarsonic acid (MAMA), 2-methyl-4-chloro-2-propionic acid (MCPA), MCPA-thioethyl, 2-methyl-4-chloro-2-propionic acid (MCPB), 2-methyl-4-chloro-2-propionic acid (mecoprop), mecoprop-P, medinotrb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metam-2-propionic acid (mefenacet), mesotrione, mesotrione, mefenacet, mefenacet-2-propionic acid (mecoprop-P), medimethoxam, mesotrione, mefenacet-2-propionic acid (mecoprop-P), medimethoxam, mesotrione, mefenacet-2-propionic acid (mecoprop-P), medimethoxam, mesotrione, mefenacet-2-propionic acid (mefenacet), mesotrione, mefenacet-2-propionic acid (mecoprop-P), medimethoxam, ...fenacet), mefenacet-2-propionic acid (mefluidide), mesotrione, mesotrione, mefenacet-2-propionic acid (mecoprop-P), medimethoxam, mesotrione, mefenacet-2-propionic acid (mecoprop-P), medimethoxam, mefenacet-2 fop), metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide bromide), methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid acid), monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, octachlorone (OCH), orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid acid), pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate cyanate), pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, and propham , propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron azosulfuron), pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, Quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, chloroacetic acid (SMA), sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid acid), sulglycapin, swep, trichloroacetic acid (TCA), tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, pyrimidine tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.

Another embodiment of the present invention is a method for controlling or preventing fungal attack. The method comprises applying an antifungal effective amount of one or more compounds of Formula I to the soil, plant, root, leaf, seed, or fungal locus, or to the site to be protected from attack (e.g., to cereal plants). The compounds are suitable for treating various plants at an antifungal level while exhibiting low phytotoxicity. The compounds can be used in a protective and/or eradication manner.

The compounds have been found to have significant fungicidal effects, particularly for agricultural use. Many of the compounds are particularly effective for use in agricultural crops and horticultural plants. Other benefits may include, but are not limited to, improving plant health; increasing plant yield (e.g., increasing biomass and/or increasing the content of valuable components); increasing plant vigor (e.g., promoting plant growth and/or promoting greener leaves); improving plant quality (e.g., increasing the content or composition of certain components); and enhancing plant tolerance to abiotic and/or biotic stresses.

It will be understood by those skilled in the art that the effectiveness of the compounds against the aforementioned fungi establishes the general utility of the compounds as fungicides.

The compounds have a broad spectrum of activity against fungicidal pathogens. Exemplary pathogens may include, but are not limited to, wheat leaf blotch (Septoriatritici, also known as Mycosphaerella graminicola), apple scab (Venturia inaequalis), and Cercospora leaf spot of sugar beets (Cercospora beticola), peanuts (Cercospora arachidicola and Cercosporidium personatum), and other crops, and black sigatoka of bananas (Mycosphaerella fujiensis). The exact amount of active substance applied depends not only on the specific active substance applied but also on the specific effect desired, the fungal species to be controlled and their growth stage, as well as the parts of the plant or other products with which the compound comes into contact. Therefore, all compounds and preparations containing the compounds may not be equally effective at similar concentrations or against the same fungal species.

The compounds are effective for use on plants in a disease-inhibiting and phytologically acceptable amount. The term "disease-inhibiting and phytologically acceptable amount" refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount typically ranges from about 0.1 to about 1000 ppm (parts per million), preferably 1 to 500 ppm. The exact concentration of the compound desired will vary depending on the fungal disease being controlled, the type of formulation employed, the method of application, the specific plant species, climatic conditions, and the like. Suitable application rates typically range from about 0.10 to about 4 pounds per acre (about 0.01 to 0.45 grams per square meter, g/ ^m2 ).

It will be apparent to the skilled artisan understanding the teachings herein that any range or desired value given herein can be expanded or changed without losing the effect sought.

Compounds of formula I can be prepared using well-known chemical methods. Intermediates not specifically mentioned in this specification are either commercially available, can be prepared by routes disclosed in the chemical literature or can be readily synthesized from commercial starting materials using standard methods.

The following examples are provided to illustrate various aspects of the compounds of the present invention and should not be construed as limiting the claims.

Example

Example 1: Preparation of 5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (1)

Step 1: 4-Amino-5-fluoro-1-(4-methoxyphenylsulfonyl)pyrimidin-2(1H)-one. To a solution of 4-amino-5-fluoro-pyrimidin-2-ol* (1.0 gram (g), 7.75 millimoles (mmol)) in acetonitrile ( _CH3CN ; 50 milliliters (mL)) was added di-N,O-trimethylsilylacetamide (BSA; 5.7 mL, 23.3 mmol), and the mixture was heated at 70°C for 1 hour (h) to give a clear solution. After cooling to room temperature, 4-methoxybenzene-1-sulfonyl chloride (1.8 g, 8.5 mmol) was added, and the mixture was stirred for 24 h. The solvent was evaporated, and the residue was partitioned between ethyl acetate (EtOAc) and brine. The organic phase was dried over magnesium sulfate (MgSO ₄ ), filtered, and evaporated to give the product as a light yellow solid (1.48 g, 64%): mp 182-5° C.; ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.40 (br s, 1H), 8.11 (d, J=5.9 Hz, 1H), 8.04-7.98 (m, 2H), 7.02-6.96 (m, 2H), 5.77 (br s, 1H), 3.88 (s, 3H); ESIMS m/z 300 ([M+H] ⁺ ).

*4-Amino-5-fluoro-pyrimidin-2-ol is commercially available.

Step 2: 5-Fluoro-4-imino-1-(4-methoxyphenylsulfonyl)-3-methyl-3,4-dihydropyrimidin-2(1H)-one. To an 8 mL screw-capped vial was added 4-amino-5-fluoro-1-(4-methoxyphenylsulfonyl)-pyrimidin-2(1H)-one (0.293 g, 0.979 mmol), anhydrous potassium carbonate ( _K2CO3 ; 0.271 _g , 1.96 mmol), and N,N-dimethylformamide (DMF; 4 mL), followed by iodomethane ( _CH3I ; 0.208 g, 1.47 mmol). The reaction vessel was sealed, and the reaction mixture was warmed to 60°C and stirred for 4 h. The reaction mixture was cooled to room temperature, diluted with EtOAc (20 mL), and washed with water ( _H2O ; 3 x 10 mL). The organic phase was dried over _MgSO₄ , filtered, and the solvent evaporated under reduced pressure. Purification by flash chromatography (silica gel ( _SiO₂ ), EtOAc/hexane gradient) gave the title compound as a pale yellow solid (36 mg, 12%): mp 158–162° C.; ¹ H NMR (400 MHz, DMSO- _d₆ ) δ 8.01 (d, J=9.22 Hz, 2H), 7.74 (d, J=5.27 Hz, 1H), 7.04 (d, J=9.23 Hz, 2H), 3.90 (s, 3H), 3.31 (s, 3H); ESIMS m/z 314 ([M+H] ^⁺ ).

Step 3: 5-Fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (1). A 25 mL screw-cap vial was charged with 5-fluoro-4-imino-1-(4-methoxyphenylsulfonyl)-3-methyl-3,4-dihydropyrimidin-2(1H)-one (80.4 mg, 0.257 mmol), trifluoroacetic acid (TFA; 16.0 mL, 215 mmol), and dimethyl sulfide (94.0 L, 1.28 mmol). The resulting solution was stirred at room temperature for 5.5 h and then concentrated to dryness by rotary evaporation at 30°C. The crude material was then dissolved in a minimum amount of methanol ( _CH3OH ; ~2 mL) and loaded onto a 5 g normal phase solid-load Isco cartridge, rinsing the stock vial with _CH3OH (3 x 1 mL). The solid cartridge was then dried under vacuum at room temperature. After drying, the product was purified by chromatography (4 g SiO ₂ column; gradient solvent from 0 to 30% CH ₃ OH in dichloromethane (CH ₂ Cl ₂ )). The material thus obtained was identified as the desired product, 4-methoxysulfonate. The free base was obtained by dissolving the material in CH ₃ OH (4 mL), adding MP-carbonate resin (345 mg, 3.03 mmol/g, 4.0 equiv), and stirring at room temperature. After stirring for 20 h, the solid resin was filtered off and then rinsed with CH ₃ OH (3 x 1 mL). After concentration under high vacuum, 5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (35.2 milligrams (mg, 96%) was obtained as a white solid with 95% purity: mp 181-184°C; ^1H NMR (400 MHz, DMSO- _d6 ) δ 7.48 (d, J = 4.1 Hz, 1H), 3.22 (s, 3H); ^13C NMR (101 MHz, DMSO- _d6 ) δ 152.19 (s), 151.86 (d, J = 27.3 Hz), 136.73 (d, J = 221.0 Hz), 129.45 (d, J = 26.0 Hz), 28.91 (s).

Example 2: Preparation of 5-fluoro-4-imino-3-(thien-2-ylmethyl)-3,4-dihydropyrimidin-2(1H)-one (2)

Step 1: 5-Fluoro-4-imino-1-((4-methoxyphenyl)sulfonyl)-3-(thiophen-2-ylmethyl)-3,4-dihydropyrimidin-2(1H)-one. To a 25 mL vial with a magnetic stirrer was added 4-amino-5-fluoro-1-((4-methoxyphenyl)sulfonyl)pyrimidin-2(1H)-one (150 mg, 0.501 mmol), thiophen-2-ylmethanol (172 mg, 1.504 mmol), triphenylphosphine ( _Ph3P ; 394 mg, 1.504 mmol), and dry tetrahydrofuran (THF; 4.204 mL). The reaction mixture was placed under a nitrogen ( _N2 ) atmosphere and cooled to ice bath temperature. After cooling for 10 minutes (min), diethyl azodicarboxylate (DEAD; 0.238 mL, 1.504 mmol) was added dropwise, and the mixture was allowed to warm to room temperature overnight. The reaction mixture was evaporated to dryness. The crude residue was purified on _SiO2 (EtOAc/hexane gradient) to give the title compound (146 mg, 73.8%) as a yellow-white wax: ^1H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 9.1 Hz, 2H), 7.84 (d, J = 1.8 Hz, 1H), 7.67 (d, J = 5.5 Hz, 1H), 7.17 (dd, J = 5.2, 1.2 Hz, 1H), 7.13 (d, J = 3.5 Hz, 1H), 7.02 (d, J = 9.1 Hz, 2H), 6.88 (dd, J = 5.1, 3.5 Hz, 1H), 5.28 (s, 2H), 3.91 (s, 3H) _; UV ( _CH2Cl2 ) _λmax : 259 nm; ESIMS m/z 396.5 ([M+H] ⁺ ).

Step 2: 5-Fluoro-4-imino-3-(thiophen-2-ylmethyl)-3,4-dihydropyrimidin-2(1H)-one (2). Dimethyl sulfide (0.122 mL, 1.64 mmol) was added to a magnetically stirred mixture of 5-fluoro-4-imino-1-((4-methoxyphenyl)sulfonyl)-3-(thiophen-2-ylmethyl)-3,4-dihydropyrimidin-2(1H)-one (130 mg, 0.329 mmol) in dry TFA (2.529 mL) in a dry 25 mL vial under argon. The reaction mixture was stirred at 23° C. for 16 h. The reaction mixture was evaporated to dryness, and the crude residue was diluted with ice water and saturated aqueous sodium bicarbonate solution and extracted with CH ₂ Cl ₂ (2×). The layers were separated, the combined organic extracts were evaporated, and the crude residue was purified on _SiO2 (EtOAc/ _{CH2Cl2 gradient} solvent) to give the title compound (15 mg, 19.2%) as a white wax: ^1H NMR (400 MHz, CDCl3 + D2O) δ 7.22 (br d, J = 3.4 Hz, 1H), 7.21 (dd, J = 5.2, 1.1 Hz, 1H), 6.94 (dd, J = 5.1, 3.5 Hz, 1H), 6.72 (d, J = 4.3 Hz, 1H), 5.38 (s, 2H);13C NMR (101 MHz, _CDCl3 + _D2O ) δ 7.22 (br d, J = 3.4 Hz, 1H), 7.21 (dd, J = 5.2, 1.1 Hz, 1H), 6.94 (dd, J = 5.1, 3.5 Hz, 1H), 6.72 (d, J = 4.3 Hz, ^1H ), 5.38 (s, 2H) _; )δ152.48(d, J=30.5Hz), 151.06(s), 138.17(s), 137.82(s), 128.48(s), 126.30(s), 125.76(s), 115.39(d, J=35.1Hz), 39.30(s); ESIMS m/z 226.3([M+H] ⁺ ), 224.4([MH] ^- ).

Example 3: Preparation of 5-fluoro-4-imino-3-(trideuterated methyl)-1H-pyrimidin-2-one (3)

Step 1: 1-(phenylsulfonyl)-5-fluoro-4-imino-3-(trideuteratedmethyl)pyrimidin-2-one. A solution of 4-amino-5-fluoro-1-(phenylsulfonyl)pyrimidin-2(1H)-one (600 mg, 2.23 mmol) (prepared as described in WO 2011/017547A by Boebel, T. et al.) in dimethylformamide (DMF; 7 mL) was treated with lithium carbonate (333 mg, 4.51 mmol) and iodomethane- _d3 (807 mg, 5.56 mmol). The reaction mixture was heated at 45°C for 3.5 h. Ethyl acetate (EtOAc; 10 mL) and saturated aqueous sodium chloride solution (10 mL) were added, and the layers were separated. The aqueous layer was extracted twice more with EtOAc (2 x 5 mL). The combined organic layers were washed with saturated aqueous sodium chloride solution (3 x 5 mL), dried ( _Na2SO4 ), _and concentrated under reduced pressure. The resulting yellow solid was purified by silica gel chromatography (elution gradient 0-80% EtOAc in hexanes) to provide the title compound (307 mg, 48%) as a white solid: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.11 (m, 2H); 7.85-7.61 (b, m, 4H); ¹⁹ F NMR (375 MHz, CDCl ₃ ) δ 158.14; ¹³ C NMR (100 MHz, CDCl ₃ ) δ 152.18, 151.91, 151.64, 142.35, 137.76, 135.56, 129.79, 129.55; ESIMS m/z 287.1 ([M+H] ⁺ ).

Step 2: 5-fluoro-4-imino-3-(trideuterated methyl)-1H-pyrimidin-2-one (3). A solution of 1-(phenylsulfonyl)-5-fluoro-4-imino-3-(trideuterated methyl)pyrimidin-2-one (360 mg, 1.26 mmol) was dissolved in a mixture of 2,2,2-trifluoroacetic acid (31.9 mmol, 2.4 mL) and dimethyl sulfide (5.9 mmol, 0.57 mL) and kept at room temperature for 2 h, then concentrated under reduced pressure. The resulting amorphous gel was purified under reduced pressure and purified by silica gel chromatography (0-50% MeOH in dichloromethane gradient solvent). After the purified product was evaporated to dryness, it was dissolved in anhydrous methanol (10 mL) and gently stirred with 1.5 g of PS-carbonate beads for 2 days. The product was then collected by vacuum filtration and evaporated to constant mass to give the title compound as a white solid (59 mg, 40%): ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 7.5 (s, 1H); ¹⁹ F NMR (375 MHz, DMSO-d ₆ ) δ 171.45; ¹³ C NMR (100 MHz, DMSO-d ₆ ) δ 152.18, 151.64, 137.76, 135.56, 129.66; ESIMS m/z 147.2 ([M+H] ⁺ ).

Example 4: Evaluation of fungicidal activity: wheat leaf spot (Mycosphaeria graminearum; anamorph: wheat leaf spot pathogen; Bayer code SEPTTR)

Wheat plants (Yuma variety) are grown in a greenhouse in a 50% mineral soil/50% soilless Metro mixture from seeds until the first leaves emerge completely, with 7-10 seedlings per pot. Before or after the fungicide treatment, these plants are inoculated with an aqueous spore suspension of the wheat leaf spot pathogen. After inoculation, the plants are maintained at 100% relative humidity (in a photic dew chamber for 1 day, then in a light dew chamber for two to three days) so that the spores germinate and infect the leaves. The plants are then transferred to the greenhouse so that the disease develops.

Example 5: Evaluation of fungicidal activity: Apple scab (Ventrinia inaequalis; Bayer code: VENTIN):

Apple seedlings (McIntosh or Golden Delicious) were planted in Metro mix and inoculated with a spore suspension containing 5 x 105 spores/ml. The plants were placed in a dew chamber at 100% relative humidity for 24 hours and then transferred to a greenhouse at 18°C to allow the disease to develop.

The following table presents the activity of representative compounds of the invention when evaluated in these experiments. The effectiveness of the test compounds in controlling disease was determined by rating the severity of the disease on treated plants and then converting the severity to percent control based on the level of disease on untreated inoculated plants.

In each case of Table I, the grade ranges are as follows:

Table I: One-day protective (1DP) and three-day curative (3DC) activity of compounds against SEPTTR at a concentration of 100 ppm

Compound SEPTTR 100PPM 1DP SEPTTR 100PPM 3DC 1 A A 2 B A 3 D D

Table II: One-day protective (1DP) activity of compounds at a concentration of 100 ppm against VENTIN

Compound VENTIN 100PPM 1DP 1 B

The present invention includes the following embodiments

Embodiment 1. Compounds of Formula I:

Where ^R1 is:

C ₁ -C ₆ alkyl optionally substituted with 1-3 R ³ ;

C ₁ -C ₆ alkenyl optionally substituted with 1-3 R ³ ;

C ₃ -C ₆ alkynyl optionally substituted with 1 to 3 R ³ ;

phenyl or benzyl, wherein each of the phenyl or benzyl groups may be optionally substituted with 1-3 R ⁴ , or substituted with a 5- or 6-membered saturated or unsaturated ring system, or substituted with a 5-6 fused ring system, or substituted with a 6-6 fused ring system, each containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ ,

-(CHR ⁵ ) _m OR ⁶ ;

-C(=O)R ⁷ ;

-C(＝S)R ⁷ ;

-C(=O)OR ⁷ ;

-C(＝S)OR ⁷ ;

-S(O) ₂ R ⁷ ;

-(CHR ⁵ ) _m N(R ⁸ )R ⁹ ;

-C(=O)N(R ⁸ )R ⁹ ; or

-C(=S)N(R ⁸ )R ⁹ ;

Where m is an integer from 1 to 3;

^R2 is:

H; or

C ₁ -C ₆ alkyl optionally substituted with R ³ ;

^R3 is independently halogen, _C1 - _C6 alkyl, C1- _C4 haloalkyl, _C1 -C4 alkoxy, _C1 - _C4 haloalkoxy, _C1 - _C4 alkylthio, C1- _C4 haloalkylthio, amino, halothio, _C1 -C3 alkylamino, _C2 - _C6 alkoxycarbonyl, _C2 - _C6 alkylcarbonyl, _C2 - _C6 alkylaminocarbonyl, hydroxy, _C3 - _C6 trialkylsilyl, or substituted with a _5- or _{6 -} membered saturated or unsaturated ring system, or substituted with a _5-6 fused ring system, or substituted with a 6-6 fused ring system, each ring system containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R;

R ⁴ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, halothio, amino, C ₁ -C ₆ alkylamino, C ₂ -C ₆ dialkylamino, C ₂ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylsulfonyl or C ₂ -C ₆ alkylcarbonyl, nitro, hydroxy, or cyano;

R ⁵ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl or benzyl, wherein each of said phenyl or benzyl groups may be optionally substituted with 1 to 3 R ⁴ ;

R ⁶ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, phenyl or benzyl, wherein each of said phenyl or benzyl groups may be optionally substituted with 1-3 R ⁴ , or substituted with a 5- or 6-membered saturated or unsaturated ring system, or substituted with a 5-6 fused ring system, or substituted with a 6-6 fused ring system, each containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ , biphenyl or naphthyl optionally substituted with 1-3 R ⁴ ;

R ⁷ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, phenyl or benzyl, wherein each of said phenyl or benzyl groups may be optionally substituted with 1-3 R ⁴ , or substituted with a 5- or 6-membered saturated or unsaturated ring system, or substituted with a 5-6 fused ring system, or substituted with a 6-6 fused ring system, each containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ , biphenyl or naphthyl optionally substituted with 1-3 R ⁴ ;

R ⁸ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, phenyl or benzyl, wherein each of said phenyl or benzyl groups may be optionally substituted with 1-3 R ⁴ , or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system, each containing 1-3 heteroatoms, wherein each ring may be optionally substituted with 1-3 R ⁴ , biphenyl or naphthyl optionally substituted with 1-3 R ⁴ ; and

R ⁹ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, or benzyl, wherein the benzyl group may be optionally substituted with 1 to 3 R ⁴ ;

Alternatively, R ⁸ and R ⁹ may together form a 5- or 6-membered saturated or unsaturated ring containing 1 to 3 heteroatoms, wherein each ring may be optionally substituted with 1 to 3 R ⁴ .

Embodiment 2. A composition for controlling fungal pathogens, comprising the compound of embodiment 1 and a phytologically acceptable carrier material.

Embodiment 3. The composition of embodiment 2, wherein the fungal pathogen is at least one of the following: apple scab (Victoria inaequalis), wheat leaf spot (Triticum truncatum), beet leaf spot (Cercospora betae), peanut leaf spot (Cercospora arachis and Cercospora globosum), and banana leaf spot (Mycosphaeria fijiensis).

Embodiment 4. A method for controlling and preventing fungal infestation on plants, comprising the steps of:

A fungicidally effective amount of at least one compound of embodiment 1 is applied to at least one of the plant, an area adjacent to the plant, soil suitable for supporting growth of the plant, roots of the plant, foliage of the plant, and seeds suitable for producing the plant.

Claims (16)

1. Compounds of formula I or their salts: Wherein ^R1 is a _C1 - _C6 alkyl group optionally substituted with ^R3 ; and ^R2 is H; ^R3 is a 5-membered unsaturated sulfur-containing ring system. 2. The compound of claim 1, wherein ^R1 is a _C1 - _C6 alkyl group and ^R2 is H. 3. The compound of claim 1, wherein it is in the form of a salt. 4. The compound of claim 3, wherein the salt is a hydrochloride, hydrobromide, or hydroiodide. 5. The compound of claim 2, wherein it is in the form of a salt. 6. The compound of claim 5, wherein the salt is a hydrochloride, hydrobromide, or hydroiodide. 7. A composition for the prevention or control of fungal pathogens, comprising a compound of any one of claims 1-6 and a botanically acceptable carrier substance. 8. The composition of claim 7, wherein the fungal pathogen is at least one of the following: apple black spot fungus, wheat leaf spot pathogen, beet causal agent, peanut causal agent, and Fiji coccidioidomyces. 9. The composition of claim 8, wherein the composition further comprises an auxiliary surfactant. 10. The composition of claim 9, wherein the auxiliary surfactant is selected from ethoxylated nonylphenol; ethoxylated synthetic alcohol or ethoxylated natural alcohol; sulfosuccinate or sulfosuccinate; ethoxylated organosiloxane; ethoxylated fatty amine; a blend of surfactant with mineral oil or vegetable oil; crop oil concentrate, i.e., 85% mineral oil + 15% emulsifier; nonylphenol ethoxylate; benzyl cocoyl dimethyl quaternary ammonium salt; a blend of petroleum hydrocarbons, alkyl esters, organic acids and anionic surfactants; _C9 - _C11 alkyl polyglycosides; phosphorylated alcohol ethoxylates; natural primary alcohols ( _C12 - _C16 ) ethoxylates; di-sec-butylphenol EO-PO block copolymers; polysiloxane-methyl-terminated compounds; nonylphenol ethoxylate + urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol synthetic ethoxylate; tallow amine ethoxylate; and PEG (400) dioleate-99. 11. A method for controlling or preventing fungal invasion on plants, the method comprising the following steps: Apply an effective amount of at least one of the compounds of any one of claims 1-6 to the plant, an area adjacent to the plant, soil suitable for supporting the growth of the plant, the roots of the plant, the leaves of the plant, and at least one of the seeds suitable for producing the plant. 12. The method of claim 11, wherein the method further comprises applying an auxiliary surfactant. 13. A method for controlling or preventing fungal invasion on plants, the method comprising the following steps: Apply an effective amount of the composition of claim 7 to the plant, an area adjacent to the plant, soil suitable for supporting the growth of the plant, the roots of the plant, the leaves of the plant, and at least one of the seeds suitable for producing the plant. 14. The method of claim 13, wherein the method further comprises applying an auxiliary surfactant. 15. Use of the compound of any one of claims 1-6 in the preparation of a fungicidal composition for preventing or controlling fungal invasion on plants. 16. An insecticide comprising the compound of any one of claims 1-6 and a second insecticide compound, wherein the second insecticide compound is selected from fungicides, insecticides, herbicides, nematicides, acaricides, arthropodicides, fungicides, or combinations thereof.