NZ620537B2 - 5-fluoro-4-imino-3-(substituted)-3,4-dihydropyrimidin-2-(1h)-one derivatives - Google Patents

Abstract

Provided are fungicidal 5-fluoro-4-imino-3-(substituted)-3,4-dihydropyrimidin-2-(1H)-one derivative compounds of the general formula I, wherein the variables are as defined in the specification. Examples of the compounds include 5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one and 5-fluoro-4-imino-3-(thiophen-2-ylmethyl)-3,4-dihydropyrimidin-2(1H)-one. -imino-3-(thiophen-2-ylmethyl)-3,4-dihydropyrimidin-2(1H)-one.

Description

wo 2013/025795 -FLUOR0IMIN0(SUBSTITUTED)-3,4-DIHYDROPYRIMIDIN-2(1H)ONE DERIVATIVES Cross Reference to Related Applications

[0001] This application claims the benefit ofU.S. Provisional Patent Application Serial No. 61/524,506 filed August 17, 2011, which is expressly incorporated by reference herein.

Background and Summary ofthe Invention Fungicides are compounds, ofnatural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. lly, no single fungicide is useful in all situations. Consequently, research is g to produce fungicides that may have better performance, are easier to use, and cost less.

The present sure relates to 3-alkylfluoroimino-3,4-dihydropyrimidin- 2(1H)one compounds and their use as fungicides. The compounds ofthe present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

[0004] One embodiment ofthe present disclosure may include compounds ofFormula I: F:CN...-H R2 ~ ' N A N 0 wherein R1is: C1-C6 alkyl ally substituted with 1-3 R3; C1-C6 alkenyl optionally substituted with 1-3 R3; C3-C6 alkynyl optionally substituted with 1-3 R3; phenyl or benzyl wherein each ofthe phenyl or the benzyl may be ally substituted with 1-3 R4, or with a 5- or ered 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 atoms wherein each ring may be optionally substituted with 1-3 R4, -(CHR5)mOR6; wo 2013/025795 -C(=O)R7; -C(=O)OR7; -C(=S)OR7; -S(0)2R7; -(CHR5)m N(R8)R9; -C(=O)N(R8)R9; or -C(=S)N(R8)R9; wherein m is an integer 1-3; R2 is: H; or C1-C6 alkyl optionally substituted with R3; R3 is independently halogen, C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1- C4 hio, C1-C4 haloalkylthio, amino, halothio, C1-C3 alkylamino, CrC6 alkoxycarbonyl, Cr C6 alkylcarbonyl, CrC6 alkylaminocarbonyl, hydroxyl, C3-C6 trialkylsilyl, 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 ning 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R; R4 is independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1- C6 alkylthio, C1-C6 haloalkylthio, io, amino, C1-C6 mino, C2-C6 dialkylamino, CrC6 alkoxycarbonyl, C1-C6 alkylsulfonyl or CrC6 alkylcarbonyl, nitro, hydroxyl, or cyano; R5 isH, C1-C6 alkyl, C1-C6 alkoxy, phenyl or benzyl wherein each ofthe benzyl or the phenyl may be optionally substituted with 1-3 R4; R6 isH, C1-C6 alkyl, CrC6 alkenyl, C3-C6 l, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, CrC6 alkylcarbonyl, phenyl or benzyl wherein each ofthe phenyl or the benzyl may be optionally substituted with 1-3 R4, or with a 5- or 6-membered saturated or unsaturated ring system, or with wo 2013/025795 -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 R4, biphenyl or naphthyl ally substituted with 1-3 R4; R7 isH, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C1-C6 kyl, C1-C6 alkoxyalkyl, phenyl or benzyl wherein each ofthe phenyl or the benzyl may be optionally substituted with 1-3 R4, or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or 6-6 fused ring system each ning 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R4, biphenyl or naphthyl optionally substituted with 1-3 R4; R8 isH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, C2-C6 alkylcarbonyl, phenyl or benzyl wherein each ofthe phenyl or the benzyl may be optionally tuted with 1-3 R4, or with a 5- or 6-membered ted or unsaturated ring system, or with a 5-6 fused ring system, or with a 6- 6 fused ring system each ning 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R4, biphenyl or naphthyl optionally substituted with 1-3 R4; and R9 isH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, CrC6 alkylcarbonyl, or benzyl, wherein the benzyl may be optionally substituted with 1-3 R4; alternatively R8 and R9 may be taken together to form a 5- or 6- membered saturated or unsaturated ring containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R4.

Another embodiment ofthe present disclosure may e a fungicidal composition for the control or prevention offungal attack comprising the compounds described below and a phytologically acceptable carrier material.

Yet r embodiment ofthe present disclosure may include a method for the l or prevention offungal attack on a plant, the method including the step ofapplying a fungicidally effective amount ofone or more ofthe compounds described below to at least one ofthe fungus, the plant, an area adjacent to the plant, and the seed adapted to produce the plant. wo 2013/025795 The term "alkyl" refers to a ed, unbranched, or cyclic carbon chain, including methyl, ethyl, propyl, butyl, pyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

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

The term "alkynyl" refers to a branched or unbranched carbon chain ning one or more triple bonds including propynyl, butynyl and the like. [001 0] As used throughout this specification, the term 'R'refers to the group consisting ofC1-s alkyl, C3-s alkenyl or C3-s alkynyl, unless stated otherwise.

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

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

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

The term "alkylsulfonyl" refers to an -SOz-R substituent.

[0015] 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, which is substituted with Cl, F, I, or Br or any combination thereof.

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

[0019] The term "trialkylsilyl" refers to -SiR3.

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

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

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

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

[0024] The term "dialkylamino" refers to a -NR2 substituent.

The term "alkoxyalkyl" refers to an alkoxy substitution on an alkyl.

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

[0028] The term "nitro" refers to a -N02 substituent. wo 2013/025795 Throughout the disclosure, reference to the compounds ofFormula I is read as also including optical isomers and salts ofFormula I, and hydrates thereof. Specifically, when Formula I ns a branched chain alkyl group, it is understood that such compounds include optical isomers and racemates thereof. Exemplary salts include: hydrochloride, hydrobromide, hydroiodide, and the like. Additionally, the compounds ofFormula I may include tautomeric forms.

Certain compounds disclosed in this document can exist as one or more isomers.

It will be appreciated by those skilled in the art that one isomer may be more active than the others. The structures disclosed in the present disclosure are drawn in only one geometric form for clarity, but are intended to represent all geometric and tautomeric forms ofthe molecule.

It is also understood by those skilled in the art that additional tution is allowable, unless otherwise noted, as long as the rules ical g and strain energy are satisfied and the product still exhibits fungicidal activity.

Another embodiment ofthe present disclosure is a use of a compound ula I, for protection ofa plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic sm, comprising the application ofa compound of Formula I, or a composition comprising the compound to soil, a plant, a part ofa plant, foliage, and/or seeds.

Additionally, another embodiment ofthe present disclosure is a composition useful for protecting a plant against attack by a athogenic organism and/or treatment ofa plant ed by a phytopathogenic sm comprising a compound ula I and a phytologically acceptable carrier material.

Additional features and advantages ofthe present invention will become apparent to those skilled in the art upon consideration ofthe following detailed description ofthe illustrative ments exemplifying the best mode of carrying out the invention as presently perceived.

Detailed Description ofthe Disclosure The compounds ofthe present disclosure may be applied by any ofa variety of known ques, either as the nds or as formulations comprising the compounds. For example, the compounds may be applied to the roots, seeds or foliage ofplants for the control of wo 25795 various fungi, t damaging the commercial value ofthe plants. The materials may be applied in the form ofany ofthe generally used formulation types, for example, as solutions, dusts, wettable powders, flowable trates, or emulsifiable concentrates.

Preferably, the compounds ofthe present disclosure are applied in the form ofa formulation, comprising one or more ofthe compounds ofFormula I with a ogically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations can be prepared according to procedures that are conventional in the agricultural al art.

[0037] The present disclosure plates all vehicles by which one or more ofthe compounds may be formulated for delivery and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or sion concentrates. As will be readily appreciated, any al to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity ofthese compounds as antifungal agents.

Wettable powders, which may be compacted to form water dispersible es, comprise an intimate mixture ofone or more ofthe compounds ofFormula I, an inert carrier and surfactants. The concentration ofthe compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight ofthe wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation ofwettable powder formulations, the compounds may be nded with any finely d solid, such as prophyllite, talc, chalk, gypsum, Fuller'searth, ite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the nd(s) and milled.

Emulsifiable concentrates ofthe compounds ofFormula I may comprise a convenient concentration, such as from about 10 weight t to about 50 weight percent of the compound, in a suitable liquid, based on the total weight ofthe concentrate. The compounds may be dissolved in an inert r, which is either a water-miscible t or a mixture of wo 2013/025795 water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form ofoil-in-water emulsions. Useful organic solvents e aromatics, especially the high-boiling naphthalenic and olefinic portions ofpetroleum such as heavy aromatic naphtha. Other c solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as xyethanol.

Emulsifiers which may be ageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend oftwo or more emulsifiers. Examples ofnonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products ofalkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl s and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) ofalkylaryl sulfonic acids, oil-soluble salts or ed polyglycol ethers and appropriate salts ofphosphated polyglycol ether. entative organic liquids which may be employed in preparing the emulsifiable concentrates ofthe compounds ofthe present invention are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted ic organic liquids such as dioctyl phthalate; ne; dialkyl amides of various fatty acids, ularly the yl amides offatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether hylene , the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, com oil, seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters ofthe above vegetable oils; and the like.

Mixtures oftwo or more organic liquids may also be employed in the ation ofthe emulsifiable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on wo 2013/025795 the combined weight ofthe dispersing agent with one or more ofthe compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in lture.

Aqueous suspensions comprise suspensions ofone or more water-insoluble compounds ofFormula I, dispersed in an aqueous vehicle at a concentration in the range from about 5 to about 50 weight percent, based on the total weight ofthe aqueous suspension.

Suspensions are prepared by finely grinding one or more ofthe compounds, and vigorously mixing the ground material into a vehicle comprised ofwater and surfactants chosen from the same types discussed above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to se the density and ity ofthe aqueous vehicle. It is often most effective to grind and mix at the same time by preparing the s mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type nizer.

Aqueous emulsions comprise emulsions ofone or more water-insoluble pesticidally active ingredients emulsified in an aqueous vehicle at a concentration typically in the range from about 5 to about 50 weight t, based on the total weight ofthe s emulsion. Ifthe pesticidally active ingredient is a solid it must be dissolved in a suitable waterimmiscible t prior to the preparation ofthe aqueous emulsion. Emulsions are prepared by emulsifying the liquid idally active ingredient or immiscible solution thereof into an aqueous medium typically with inclusion of surfactants that aid in the formation and stabilization ofthe emulsion as described above. This is often accomplished with the aid ofvigorous mixing provided by high shear mixers or homogenizers.

The compounds ofFormula I can also be applied as granular formulations, which are particularly useful for applications to the soil. ar formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight ofthe granular formulation ofthe compound(s), dispersed in an inert carrier which consists entirely or in large part ofcoarsely d inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive nce. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular r which has been preformed to the appropriate particle size, in the range offrom about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. Such formulations may also be prepared by wo 25795 making a dough or paste ofthe carrier and the compound and solvent, and crushing and drying to obtain the d granular particle.

Dusts containing the compounds ofFormula I may be prepared by intimately mixing one or more ofthe compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight t ofthe compounds, based on the total weight of the dust.

The ations may additionally contain adjuvant surfactants to enhance deposition, g and ation ofthe compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component ofthe formulation or as a tank mix. The amount ofadjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume ofwater, preferably 0.05 to 0.5 volume t. Suitable adjuvant surfactants include, but are not d to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts ofthe esters or sulfosuccinic acids, ethoxylated organosilicones, ethoxylated fatty , blends ofsurfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%) +emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend ofpetroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9-Cn alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol( 6) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrrate; emulsified methylated seed oil; tridecyl l (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. The formulations may also include oil-in-water ons such as those disclosed in U.S. Patent Application Serial No. 11/495,228, the disclosure ofwhich is expressly incorporated by reference herein.

[0047] The formulations may optionally include ations that contain other pesticidal compounds. Such additional pesticidal compounds may be fungicides, icides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereofthat are compatible with the compounds ofthe present invention in the medium selected for application, and not antagonistic to the activity ofthe present compounds. Accordingly, in such embodiments, the other pesticidal compound is employed as a supplemental toxicant for the wo 2013/025795 same or for a different pesticidal use. The compounds ofFormula I and the idal compound in the combination can generally be present in a weight ratio offrom 1: 100 to 100: 1.

The compounds ofthe present disclosure may also be ed with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds ofthe t sure are often applied in ction with one or more other fungicides to control a wider variety ofundesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank mixed with the other fungicide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2- phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, brom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, benalaxyl, benomyl, benthiavalicarbisopropyl , benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, e, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, enamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis- ocarbamate), dichlofluanid, dichlorophen, ymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, nazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph e, clodine, e free base, edifenphos, enestrobin, epoxiconazole, xam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, , ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, tadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, licarb, isoprothiolane, isopyrazam, isotianil, laminarin, kasugamycin, wo 2013/025795 kasugamycin hydrochloride hydrate, im-methyl, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, xyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl , methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, hal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, yl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyllaurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium yquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, onazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, nox, thanil, pyriofenone, pyroquilon, quinoclamine, yfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2- phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYPZ071 , SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, il, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, lazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)-N-(3 ,5-dichlorophenyl)(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1, 1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4- dinitronaphthalene, 1-chloronitropropane, 2-(2-heptadecylimidazolinyl)ethanol, 2,3- dihydrophenyl-1 ,4-dithi-ine 1,1 ,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2- methoxyethylmercury chloride, 2-methoxyethylmercury silicate, hlorophenyl) methylrhodanine, 4-(2-nitropropenyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, orf, binapacryl, thylmercury) sulfate, bis(tributyltin) oxide, bate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, nthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, cyclafuramid, wo 2013/025795 cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, nosulf, nil, fenitropan, fluotrimazole, furcarbanil, furconazole, azole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, loric anhydride, myclozolin, N-3,5-dichlorophenyl-succinimide, Nnitrophenylitaconimide, cin, N-ethylmercuriotoluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, picolinamide UK- I 0 2A and derivatives f, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, fur, etol, quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, and zarilamide, and any combinations thereof.

[0049] Additionally, the nds ofthe present invention may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations fthat are compatible with the compounds ofthe present invention in the medium selected for application, and not antagonistic to the activity ofthe present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds ofthe t disclosure may be applied in conjunction with one or more other pesticides to control a wider variety ofundesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be ated with the other pesticide(s), tank mixed with the other pesticide(s) or applied tially with the other pesticide(s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, on, acetoprole, acrinathrin, acrylonitrile, alanycarb, rb, aldoxycarb, aldrin, allethrin, midin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphosethyl , azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, wo 2013/025795 bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, uran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, ntraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, hoxim, razophos, yrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, n II, cinerins, hrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, enphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, rothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, ate, DDT, decarbofuran, deltamethrin, demephion, demephion-0, ion-S, demeton, n-methyl, demeton-0, demetonmethyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, rvos, 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, dlimonene , DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, ion, endrin, EPN, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, prox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, othion, fenobucarb, fenoxacrim, fenoxycarb, ithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, erim, flufenoxuron, flufenprox, flufiprole, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, carb, imidacloprid, imiprothrin, indoxacarb, iodomethane, wo 2013/025795 2012/050930 IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, in I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, hos, e, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, meperfluthrin, folan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl ocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, rbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, ate, oxamyl, oxydemeton-methyl, rofos, oxydisulfoton, paradichlorobenzene , parathion, parathion-methyl, penfluron, pentachlorophenol, hrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, taphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, ene II, precocene III, primidophos, ofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, rin 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 uorosilicate, sodium thiocyanate, ide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, rimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, carb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, ethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, wo 2013/025795 2012/050930 trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations Additionally, the compounds ofthe present invention may be combined with herbicides that are compatible with the compounds ofthe present invention in the medium ed for application, and not antagonistic to the activity ofthe present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds ofthe present disclosure may be applied in conjunction with one or more herbicides to l a wide y of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank mixed with the herbicide(s) or applied tially with the herbicide(s). Typical 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; P; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, yralid, amiprofos-methyl, amitrole, um sulfamate, os, anisuron, asulam, atraton, atrazine, azafenidin, lfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, ram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, razon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium te, calcium cyanamide, cambendichlor, ulam, carbetamide, azole chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, turon, enac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlomitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, dim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, wo 2013/025795 delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, rprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, perate, dimethachlor, ametryn, dimethenamid, dimethenamid-P, no, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, amid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ate, mesate, ethoxyfen, ethoxysulfuron, etinofen, omid, zanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, ropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, iuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, urate, hexazinone, imazamethabenz, imazamox, ic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, n, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, lfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl e, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, chlor, lam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, clofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, pebulate, wo 2013/025795 pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, azone, perfluidone, amid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, ium arsenite, potassium azide, potassium cyanate, achlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, focarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, sulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, fol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, enacil, S-metolachlor, ylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, trazone, sulfometuron, sulfosulfuron, sulfuric acid, capin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, late, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, sime, trihydroxytriazine, trimeturon, tripropindan, tritac tritosulfuron, vemolate, and xylachlor.

Another embodiment ofthe t disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, seed or locus ofthe fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal plants), a idally ive amount ofone or more ofthe compounds of Formula I. The compounds are le for treatment ofvarious plants at fungicidal levels, while ting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.

The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many ofthe compounds are particularly effective for use with agricultural crops and horticultural plants. Additional benefits may include, but are not limited to, improving wo 2013/025795 the health ofa plant; improving the yield ofa plant (e.g. increased biomass and/or increased content ofvaluable ingredients); improving the vigor ofa plant (e.g. ed plant growth and/or greener ); improving the quality ofa plant (e.g. improved content or composition of certain ingredients); and improving the tolerance to abiotic and/or biotic stress ofthe plant.

[0053] It will be understood by those in the art that the efficacy ofthe compound for the foregoing fungi establishes the general utility ofthe compounds as fungicides.

The compounds have broad ranges vity against fungal pathogens.

Exemplary pathogens may include, but are not limited to, wheat leafblotch (Septaria i, also known as Mycosphaerella graminicola), apple scab (Venturia inaequalis), and Cercospora leaf spots of sugar beets (Cercospora beticola), ots ofpeanut (Cercospora arachidicola and Cercosporidium personatum) and other crops, and black sigatoka ofbananas (Mycosphaerella fujiensis). The exact amount ofthe active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage ofgrowth thereof, as well as the part ofthe plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal s.

The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term se-inhibiting and phytologically acceptable amount" refers to an amount ofa compound that kills or ts the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will lly be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being red. The exact amount ofa compound required varies with the fungal e to be controlled, the type of formulation employed, the method ofapplication, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m2).

Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding ofthe teachings herein.

The compounds ofFormula I may be made using well-known chemical procedures. ediates not specifically mentioned in this disclosure are either commercially wo 2013/025795 available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.

The following examples are presented to illustrate the various aspects ofthe compounds ofthe present disclosure and should not be construed as limitations to the claims.

[0059] Example 1: Preparation of5-fluoroiminomethyl-3,4-dihydropyrimidin- 2(1H)-one (1) F~NH HN~N~O Step 1: 4-Aminofluoro(4-methoxyphenylsulfonyl)pyrimidin-2(1H)-one. To 4-amino fluoro-pyrimidinol* (1.0 grams (g), 7.75 millimoles (mmol)) in acetonitrile ; 50 milliliters (mL)) was added O-trimethylsilylacetamide (BSA; 5.7 mL, 23.3 mmol) and the mixture was heated at 70 oc for 1 hour (h) resulting in a clear solution. After cooling to room ature, oxybenzenesulfonyl 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 c phase was dried over magnesium e (MgS04), filtered, and evaporated to yield the product as a pale yellow solid (1.48 g, 64%): mp 182-5 oc; 1HNMR(300 MHz, CDCh) 8 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+Ht). *4-Aminofluoro-pyrimidinol can be purchased commercially.

Step 2: 5-Fluoroimino(4-methoxyphenylsulfonyl)methyl-3,4-dihydropyrimidin-2(1H)- one. To a 8 mL screw capped vial were added 4-aminofluoro(4-methoxyphenylsulfonyl)- pyrimidin-2(1H)-one (0.293 g, 0.979 mmol), anhydrous potassium carbonate (K2C03; 0.271 g, wo 2013/025795 1.96 mmol), and methylformamide (DMF; 4 mL), ed by iodomethane (CH3I; 0.208 g, 1.47 mmol). The reaction vessel was sealed, and the reaction mixture was warmed to 60 oc and stirred for 4 h. The reaction mixture was cooled to room temperature, diluted with EtOAc (20 mL), and washed with water (H20; 3 x 10 mL). The organic phase was dried over MgS04, filtered, and the solvent evaporated under d pressure. Purification by flash tography (silica gel (Si02), EtOAc/Hexanes gradient) afforded the title compound as a pale yellow solid (36 mg, 12%): mp 158-162 oc; 1H NMR (400 MHz, DMSO-d6) 8 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+Ht).

Step 3: 5-Fluoroiminomethyl-3,4-dihydropyrimidin-2(1H)-one (1). A 25 mL screw capped vial was charged with 5-fluoroimino(4-methoxyphenylsulfonyl)methyl-3,4- dihydropyrimidin-2(1H)-one (80.4 mg, 0.257 mmol), trifluoroacetic acid (TFA; 16.0 mL, 215 mmol), and dimethylsulfide (94.0 ).lL, 1.28 mmol). The resulting solution was allowed to stir at room temperature for 5.5 hand was then trated to dryness by rotary evaporation at 30 °C.

The crude material was then dissolved in a minimal amount ofmethanol (CH30H; ~2 mL) and loaded onto a 5 g normal phase solid load Isco cartridge, rinsing the source vial with CH30H (3 x 1 mL). The solid cartridge was then dried under vacuum at room temperature. After drying, the product was ed by chromatography ( 4 g Si02 column; 0 to 30% CH30H in dichloromethane (CH2Clz) gradient). The material thus obtained was ined to be the 4- methoxysulfonic acid salt ofthe desired product. The free base was obtained by dissolving the material in CH30H (4 mL), adding MP-carbonate resin (345 mg, 3.03 mmol/g, 4.0 equiv), and ng to stir at room temerature. After stirring for 20 h, the solid resin was filtered offand rinsed with CH30H (3 x 1 mL). After contentration under high vacuum, roimino methyl-3,4-dihydropyrimidin-2(1H)-one (35.2 milligrams (mg), 96%) was otained as a 95% pure white solid: mp 181-184 oc; 1H NMR (400 MHz, DMSO-d6) 8 7.48 (d, J = 4.1 Hz, 1H), 3.22 (s, 3H); 13C NMR (101 MHz, DMSO-d6) 8 152.19 (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 of5-fluoroimino(thiophenylmethyl)-3,4- dihydropyrimidin-2(1H)-one (2) wo 2013/025795 Step 1: 5-Fluoroimino((4-methoxyphenyl)sulfonyl)(thiophenylmethyl)-3,4- dihydropyrimidin-2(1H)-one. To a 25 mL vial with magnetic stirring were added 4-amino fluoro((4-methoxyphenyl)sulfonyl)pyrimidin-2(1H)-one (150 mg, 0.501 mmol), thiophen ylmethanol (172 mg, 1.504 mmol), triphenylphosphine (Ph3P; 394 mg, 1.504 mmol) and dry tetrahydrofuran (THF; 4.204 mL). The on mixture was placed under nitrogen (N2) atmosphere and cooled to ice-bath temperature. After cooling 10 minutes (min), diethylazodicarboxylate (DEAD; 0.238 mL, 1.504 mmol) was added dropwise and the mixture was d to warm to room temperature overnight. The reaction mixture was evaporated to dryness. The crude residue was purified on Si02 (EtOAc/hexanes gradient) to provide the title compound as a -white wax (146 mg, 73.8%): 1H NMR (400 MHz, CDCl3) 8 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 ) Amax: 259 nm; ESIMS m/z 396.5 ([M+Ht).

Step 2: 5-Fluoroimino(thiophenylmethyl)-3,4-dihydropyrimidin-2(1H)-one (2). To a magnetically stirred e of5-fluoroimino((4-methoxyphenyl)sulfonyl)(thiophen ylmethyl)-3,4-dihydropyrimidin-2(1H)-one (130 mg, 0.329 mmol) in dry TFA (2.529 mL) was added dimethyl sulfide (0.122 mL, 1.64 mmol) in a dry 25 mL vial under Argon atmosphere.

The reaction mixture was stirred at 23 oc for 16 h. The reaction mixture was evaporated to dryness and the crude residue was diluted with ice-water and aqueous saturated sodium bicarbonate solution and extracted with CH2Cb (2x). The layers were separated, the combined wo 2013/025795 organic extracts were evaporated, and the crude residue was purified on Si02 (EtOAc/ eH2eb gradient) to afford the title compound as an ite wax (15 mg, 19.2%): 1H NMR (400 MHz, eDeh + D20) 8 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); Be NMR (101 MHz, eDeh) 8 152.48 (d, J= 30.5 Hz), 151.06 (s), 138.17 (s), 137.82 (s), 128.48 (s), 126.30 (s), 125.76 (s), 115.39 (d,J= 35.1 Hz), 39.30 (s); ESIMS m/z 226.3 ([M+Ht), 224.4 ([M-H]} Example 3: Preparation of5-fluoroimino(trideuteriomethyl)-1H-pyrimidin- 2-one (3) Step 1: 1-(Benzenesulfonyl)fluoroimino(trideuteriomethyl)pyrimidinone. A solution of4-aminofluoro(phenylsulfonyl)pyrimidin-2(1H)-one (600 mg, 2.23 mmol) (prepared as described in Boebel, T. et al. A) 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 e was heated at 45 oe for 3.5 h. Ethyl acetate (EtOAc; 10 mL) and saturated s sodium chloride solution (10 mL) were added and the layers 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 4) and concentrated under d pressure. The resulting yellow solid was purified by silica gel chromatography (eluting gradient of0-80% EtOAc in hexanes) to yield the title compound as a white solid (307 mg, 48%): 1H NMR (400 MHz, eDeh) 8 8.11 (m, 2H); 7.85-7.61 (b, m, 4H); 19F NMR (375 MHz, eDeh) 8 ; Be NMR (100 MHz, eDeh) 8 152.18, 151.91, 151.64, 142.35, 137.76, 135.56, 129.79, 129.55; ESIMS m/z 287.1 ([M+Ht). wo 2013/025795 2012/050930 Step 2: 5-Fluoroimino(trideuteriomethyl)-1H-pyrimidinone (3). A solution of 1- (benzenesulfonyl)fluoroimino(trideuteriomethyl)pyrimidinone (3 60 mg, 1.26 mmol) was dissolved in a mixture of2,2,2-trifluoroacetic acid (31.9 mmol, 2.4 mL) and yl sulfide (5.9 mmol, 0.57 mL) for 2 hat room temperature and concentrated under reduced pressure. The resulting amorphous gel was purified under reduced re and purified by silica gel chromatography (eluting gradient from 0-50% MeOH in dichloromethane). After evaporating the purified product to dryness, it was dissolved in anhydrous methanol (10 mL) and d gently for 2 days with 1.5 g ofPS-carbonate beads. The product was then collected by vacuum filtration and evaporated to constant mass to yield the title compound as a white solid (59 mg, 40%): 1H NMR (400 MHz, DMSO-d 6) 8 7.5 (s, 1H); 19F NMR (375 MHz, DMSO-d6) o 171.45; 13C NMR (100 MHz, DMSO-d6) o 152.18, 151.64, 137.76, 135.56, 129.66; ESIMS m/z 147.2 ([M+Ht).

Example 4: Evaluation ofFungicidal Activity: LeafBlotch t (Mycasphaerella graminicala; anamorph: Septaria tritici; Bayer code SEPTTR) Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% l soil/50% soil-less Metro mix until the first leafwas fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension ofSeptaria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew r) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse for disease to develop.

Example 5: Evaluation ofFungicidal Activity: Apple Scab ria inaequalis; Bayer code VENTIN): Apple seedlings (Mcintosh or Golden Delicious) were grown in Metro mix and inoculated with a spore suspension containing 5 x 105 spore/mi. Plants were placed in a dew room for 24 hours with 100% ve humidity and then transferred to a greenhouse with a temperature of 18 oc for disease to develop.

The following table presents the activity oftypical compounds ofthe present disclosure when evaluated in these experiments. The effectiveness ofthe test compounds in 1001365710 controlling disease was determined by assessing the severity of disease on treated plants, then converting the severity to percent control based on the level of disease on untreated, inoculated In each case of Table I the rating scale is as s: % Disease Control Rating 76-100 A 51—75 B 26-50 C 0—25 D Not Tested E TABLE I: One—Day Protectant (1 DP) and Three—Day Curative (3DC) Activity of Compounds on SEPTTR at 100 ppm SEPTTR SEPTTR 100 100 cmpd PPM PPM lDP 3DC 1 A | A 2 B | A 3 D l D TABLE II: One—Day Protectant (lDP) ty of Compound on VENTIN at 100 ppm VENTlN Cmpd 1 B Reference to any prior art in the specification is not, and should not be taken as, an acknowledgment or any form of suggestion that this prior art forms part of the common general knowledge in New Zealand or any other jurisdiction. 1001608519

Claims (24)

WHAT IS CLAIMED IS:

1. A compound of Formula I: N 1T1 0 FormulaI wherein R1 is: C1—C6 alkyl optionally tuted with 1—3 R3; C1—C6 l optionally substituted with 1—3 R3; C3—C6 alkynyl optionally substituted with 1—3 R3; phenyl or benzyl wherein each ofthe phenyl or the benzyl may be optionally substituted with 1—3 R4, or with a 5— or 6—membercd saturated or unsaturated ring system, or with a 5— 6 fused ring , or with a 6—6 fused ring system each ning 1—3 heteroatoms wherein each ring may be optionally substituted with 1—3 R4, ~(CHR5)mOR(’; ~C<=O>R7; -C(=S)R7; —C(=O)OR7; —C(=S)OR7; -S(O)2R7; “(CHRS)”, N(R8)R9; —C(:O)N(R8)R9; or —C<=S)N(R8)R9; wherein m is an integer 1—3; R2 is: H; or C1-C6 alkyl optionally substituted with R3; R3 is independently halogen, C1—C6 alkyl, C1-C4 haloalkyl, C1—C4 alkoxy, C1—C4 haloalkoxy, C1- 1001608519 C4 alkylthio, C1-C4 kylthio, amino, halothio, C1-C3 alkylamino, C2-C6 alkoxycarbonyl, C2- C6 alkylcarbonyl, C2—C6 minocarbonyl, hydroxyl, C3-C5 trialkylsilyl, 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 R4; R4 is independently halogen, C1—C6 alkyl, C1—C6 haloalkyl, C1—C6 alkoxy, C1—C6 haloalkoxy, C1- C6 alkylthio, C1—C6 haloalkylthio, halothio, amino, C1—C6 alkylamino, C2—C6 dialkylamino, C2—C6 alkoxycarbonyl, C1-C6 alkylsulfonyl or C2—C6 alkylcarbonyl, nitro, hydroxyl, or cyano; R5 is H, C1-C6 alkyl, C1—C6 alkoxy, phenyl or benzyl wherein each ofthe benzyl or the phenyl may be optionally substituted with 1—3 R4; R6 is H, C1—C6 alkyl, C3-C6 alkenyl, C3—C6 alkynyl, C1—C6 haloalkyl, C1—C6 alkoxyalkyl, C2-C6 arbonyl, phenyl or benzyl wherein each ofthe phenyl or the benzyl may be optionally substituted with 1—3 R4, or with a 5- or ered saturated or unsaturated ring system, or with 5—6 fused ring system, or with a 6—6 fused ring system each containing 1—3 heteroatoms n each ring may be optionally substituted with 1—3 R4, biphenyl or naphthyl optionally substituted with 1—3 R4; R7 is H, C1-C6 alkyl, C2—C6 alkenyl, C3—C6 alkynyl, C1—C6 haloalkyl, C1—C6 alkoxyalkyl, phenyl or benzyl n each ofthe phenyl or the benzyl may be optionally substituted with 1—3 R4, or with a 5— or 6—membered saturated or rated ring system, or with a 5—6 fused ring system, or 6—6 fused ring system each containing 1—3 heteroatoms n each ring may be optionally substituted with 1—3 R4, biphenyl or naphthyl optionally substituted with 1-3 R4; R8 is H, C1-C5 alkyl, C1—C6 haloalkyl, C1-C6 alkoxyalkyl, C2—C6 alkylcarbonyl, phenyl or benzyl n each of the phenyl or the benzyl may be optionally substituted with 1—3 R4, 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 R4, biphenyl or naphthyl optionally substituted with 1—3 R4; and 1001608519 R9 is H, C1—C6 alkyl, C1-C6 haloalkyl, C1—C6 alkoxyalkyl, C2-C6 alkylcarbonyl, or benzyl, wherein the benzyl may be optionally substituted with 1—3 R4; alternatively R8 and R9 may be taken together to form a 5- or 6- membered saturated or unsaturated ring containing 1—3 heteroatoms wherein each ring may be optionally substituted with 1-3 R4; or a salt or hydrate thereof.

2. The nd m 1, wherein R2 is H.

3. The nd of claim 1 or 2, wherein R1 is C1~C6 alkyl optionally substituted with 1—3

4. The compound of any one ofclaims 1 to 3, wherein R1 is methyl.

5. The compound ofany one ofclaims l to 4, wherein RI is methyl substituted with 1-3 R3.

6. The compound ofclaim 5, wherein R1 is methyl substituted with 1 R3.

7. The compound of claim 5 or 6, wherein R3 is a 5-membered ring system.

8. The nd of claim 7, wherein the 5—membered ring system is rated.

9. The compound of any one of claims 5 to 8, wherein R3 is thiophenyl.

10. The compound of claim 1, wherein the compound is 5—fluoroimino-3~methyl-3,4- dihydropyrimidin—2( e.

11. The compound of claim 1, wherein the compound is 5—fluoroimino(thiophen~2- ylmethyl)-3,4-dihydropyrimidin~2(1H)-one. 1001608519

12. A compound of the following structure: /U\ 093 HN N/ F or a salt or hydrate thereof.

13. A composition for the control ofa fungal pathogen including the compound ofany one of claims 1 to 12 and a phytologically acceptable carrier material.

14. The composition ofclaim 13, wherein the fungal pathogen is at least one oprple Scab (Vemuria inaequalis), Leal‘Blotch of Wheat (Septoria tritici), Leaf Spot ofSugarbeets (Cercospora belicala), Leaf Spots 0f Peanut (Cercospora arachidicola and Cercosporidium pe/‘sonalum ), and Black ka of Banana (Mycasplmercllafijiemis).

15. A method for the l and prevention of fungal attack on a plant, the method including the steps of: applying a fungicidally effective amount of at least one ofthe compounds ofany one of claims 1 to 12 to at least one ofthe plant, an area adjacent to the plant, soil adapted to support growth ofthe plant, a root ofthe plant, foliage of the plant, and a seed adapted to produce the plant.

16. A idal formulation comprising the compound of any one of claims 1 to 12 and a second pesticidal nd selected from the group consisting of fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides, or combinations thereof.

17. The idal formulation of claim 16, n the weight ratio of the compound of one of Claims 1 to 12 to the second pesticidal compound is from 1:100 to 100:1. 1001608519

18. The pesticidal formulation of claim 17, wherein the second pesticidal compound is a fungicidal compound selected from the group consisting of: 2—(thiocyanatomethylthi0)- benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimyein, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, xyl, l, avalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin—S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, e, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, nil, cyproconazole, inil, dazomet, debacarb, diammonium ethylenebis—(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, dilenzoquat ion, dillumetorim, dimethomorph, dimoxystrobin, nazole, diniconazole—M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpielonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, lludioxonil, flumorph, fluopicolidc, fluopyram, lluoroimide, fluoxastrobin, fluquinconazole, zole, llusulfamide, flutianil, anil, flutriafol, fluxapyroxad, lolpet, formaldehyde, fosetyl, fosetyl—aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, sodium tetrathiocarbonate (GY—8 l ), hexaehlorobenzene, nazole, zol, imazalil, imazalil sulfate, imibenconazole, iminoetadine, iminoetadine triacetate, iminoctadine tris(a1besilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, laminarin, kasugamycin, kasugamycin hydrochloride e, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinoeap, mercuric chloride, mercuric oxide, mercurous de, metalaxyl, metalaxyl-M, metam, metam-ammonium, potassium, metam-sodium, metconazole, methasulfocarb, methyl , methyl isothioeyanate, metiram, metominostrobin, metrafenone, mildiomyein, utanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofuraee, oleic acid (fatty , orysastrobin, oxadixyl, copper, oxpoeonazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, 1001608519 pentachlorophenyl e, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, oraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, lamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2—phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, trobin (SYP—ZO71), 3—(5—(4— chlorophenyl)—2,3-dimethyl-3—isoxazolidinyl)pyridine (SYP—ZO48), tar oils, tebuconazole, tebulloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate~methyl, thiram, tiadinil, tolclofos—methyl, tolylfluanid, triadimel’on, menol, xide, tricyclazole, orph, trifloxystrobin, triflumizole, ine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, de, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)——N- (3,S-dichlorophenyl)~2—(methoxymethyl)—succinimide, 1,2-dichloropropane, 1,3—dichloro- l,l,3,3—tetrafluoroacetone hydrate, l-chloro~2,4-dinitronaphthalene, l-chloro—2—nitropropane, 2- tadecyl—2—imidazolin— l —yl)ethanol, 2,3—dihydro—5—phenyl—l ,4-dithi—ine l, 1,4,4—tetraoxide, 2—methoxyethylmercury acetate, 2—methoxyethylmercury de, 2—methoxyethylmercury silicate, 3—(4-chlorophenyl)—5-methylrhodanine, 4—(2—nitroprop—l —enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, on (Bayer 32394), nil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, zole, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, irimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, diethyl (4-methylbenzyl)phosphonate (EBP), [ethoxy(phenylMethylsulfanyl)phosphoryl]benzene (ESBP), etaconazole, etem, ethirim, fenaminosulf, nil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, 5-Chlorophenyl-3H—l,2—dithiol- 3-one (Hercules 3944), hexylthiofos, 2-methoxy-5—aminopyridine (ICIA0858), isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, 1001608519 metsulfovax, , loric anhydride, myclozolin, N-3,5-dichloropheny1~succinimide, N- 3-nitrophenylitaconimide, natamycin, N—ethylmercuriotoluenesulfonanilide, nickel bis(dimethyldithiocarbamate), 2,3,4,4,5,5,6,6—octachlorocyclohexen—l-one (OCH), phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, picolinamide, (3S,7R)-8—benzyl-3—{[(3-hydroxy-4—methoxypyridin—2~y1)carbonyl]amino}—6—methyl—4,9—diox0— 1,5-dioxonan-7—yl 2-methylpropanoate (UK-2A), prothiocarb; prothiocarb hydrochloride, rbolid, nitril, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, amid, quinconazole, rabenzazole, salicylanilide, l—(4—chlorophenyl)(lH-l,2,4—triazol—l— yl)cycloheptan—l -Ol (SSF—109), sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, id, triamiphos, triarimol, triazbutil, trichlamide, urbacid, and zarilamide, and any ations thereof.

19. The pesticidal formulation of claim 17, n the second pesticidal compound is a pesticide compound selected from the group consisting of: 1,2—dichloropropane, abamectin, acephatc, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ccdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, hiphos, azinphos—ethyl, azinphos—methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, ylluthrin, beta— cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluoron, borax, boric acid, bromfenvinfos, bromocyclen, 2,2,2—trichloro—1,1—ethanediyl)bis(4— bromobenzene) (bromo—DDT), bromophos, bromophos~ethyl, bufencarb, ezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon hloride, carbophenothion, ulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, yrifos, yrifos—methyl, chlorthiophos, chromafenozide, cinerin I, cinerin H, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, enphos, cyanophos, cyanthoate, 8519 aniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, othrin, cyromazine, cythioate, dichlorodiphenyltrichloroethane (DDT), decarbofuran, deltamethrin, demephion, demephion-O, demephion~S, demeton, demeton—methyl, n-O, demeton—O- methyl, n-S, demeton-S—methyl, demeton—S—methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, nzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex—diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d—limonene, dinitro—ortho—cresol (DNOC), DNOC—ammonium, DNOC—potassium, odium, doramectin, ecdysterone, emamectin, tin te, p—(ethylthio)phenyl methylcarbamate (EMPC), empenthrin, endosulfan, endothion, endrin, O-ethyl O—(4—nitrophenyl) phenylphosphonothioate (EPN), epo fenonane, eprinomectin, esdepallethrine, esfenvalerate, s, ethiol‘encarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl—DDD, ne dibromide, ethylene dichloride, ethylene oxide, etofenprox, etriml’os, dixanthogen (EXD), lamphur, fenamiphos, fenazaflor, fenchlorphos, acarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, ithrin, fenpropathrin, fensulfothion, fenthion, fenthion—ethyl, fenvalerate, fipronil, flonicamid, iamide, flucofuron, flucycloxuron, llucythrinate, flufenerim, flufenoxuron, flufenprox, flufiprolc, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, Formparanate, formparanate hydrochloride, fosmethilan, fospiratc, fosthietan, furathiocarb, furethrin, gamma—cyhalothrin, gamma-HCH, halfenprox, halofenozide, (hexachlorocyclohexane (HCH), dieldrin , heptachlor, heptenophos, heterophos, hexaflumuron, (lR,4$,4aS,SS,8R,8aR)—l,2,3,4,10,10—hexachloro—l ,4,4a,5,8,8a—hexahydro- 1,4:5,8—dimethanonaphthalene (HHDN), hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, thane, S-[(Ethylsulfinyl)methyl] 0,0— bis(1—methylethyl)ester (IPSP), isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin,jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone ILjuvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, hos, lindane, os, lufenuron, lythidathion, malathion, malonoben, mazidox, am, mecarphon, menazon, meperfluthrin, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, 8519 methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, arb, metoxadiazone, mevinphos, mexacarbate, milbemectin, ycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, acarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, rofos, ulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluoron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim—methyl, pirimetaphos, pirimicarb, pirimiphos~ethyl, pirimiphos-methyl, potassium arsenite, potassium anate, pp'—DDT, prallethrin, precocene 1, precocene ll, precocene Ill, primidophos, profenofos, prolluralin, promacyl, promecarb, propaphos, amphos, propoxur, prothidathion, prothiofos, prothoate, fenbute, pyraclofos, pyral’luprole, pyrazophos, pyrcsmethrin, pyrethrin l, pyrethrin ll, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, a, quinalphos, quinalphos—methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silalluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanatc, sophamide, spinetoram, spinosad, spiromcsifen, spiroletramat, sulcofuron, sulcofur0n~sodium, sullluramid, sulfotcp, sulfoxaflor, sulfuryl fluoride, sulprofos, tau—lluvalinate, tazimcarb, 1,1 ’—(2,2~dichlor0ethylidene) bis(4—chloro— (9C1) (TDE), tebufenozide, tebufenpyrad, tebupirimfos, te'flubenzuron, hrin, temephos, tetraethyl diphosphate (TEPP), terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta— cypcrmelhrin, thiacloprid, thoxam, thicrofos, rboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap—disodium, thiosultap— monosodium, thuringiensin, tolfenpyrad, tralomethrin, uthrin, transpermethrin, thene, triazamate, triazophos, trichlorfon, trichlormetaphos—3, trichloronat, trifenofos, muron, trimethacarb, triprene, vamidothion, vaniliprole, 3,5-dimethylphenyl methylcarbamate (XMC), xylylcarb, zeta-cypermethrin, ofos, and any combinations thereof.

20. The pesticidal formulation of claim 17, wherein the second pesticidal compound is a ide compound selected from the group consisting of: 4—chlorophenoxyaceticacid (4-CPA); 4-(4—chlor0phenoxy)butyric acid (4-CPB); 2—(4-chlorophenoxy)propanoic acid (4-CPP); 2,4— 1001608519 dichlorophenoxyacetic acid (2,4-D); 3,4—dichlorophenoxyacetic acid (3,4-DA); 4—(2,4- dichlorophenoxy)butyric acid (2,4-DB); —dichlorophenoxy)butyric acid (3,4—DB); 2-(2,4- dichlorophenoxy)ethyl benzoate (2,4—DEB); tris[2-(2,4—dichlorophenoxy)ethyl] phosphite (2,4— DEP); -dichlorophenoxy) propionic acid (3,4-DP); 2,3,6—trichlorobenzoic acid (2,3,6-TBA); 2,4,5—Trichlorophenoxyacetic acid (2,4,5-T); 4~(2,4,5-trichlorophenoxy)butanoic acid —TB); acetochlor, acifluorfen, aclonifen, acrolein, or, allidochlor, alloxydim, allyl alcohol, , ametridione, ametryn, amibuzin, bazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos—methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotrync, barban, butan-Z—yl N—(3— chlorophcnyl)carbamatc (BCPC), bcl‘lubutamid, bcnazolin, bencarbazonc, benfluralin, bcnfurcsate, bensulluron, bensulide, bentazonc, benzadox, benzfendizone, ram, benzobicyclon, benzolenap, benzofluor, benzoylprop, benzlhiazuron, bicyclopyronc, bifcnox, bilanafos, bispyribac, borax, bi‘omacil, bromobonil, bromobutidc, bromofenoxim, bromoxynil, brompyrazon, butachlor, nacil, butamifos, butcnachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambcndichlor, carbasulam, carbetamidc, carboxazolc chlorprocarb, carfcntrazone, 2-chlor0— N,N—diethylacclamide , 2—chloroethyl hlorophcnyl)carbamate (CEPC), chlomethoxylcn, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chlorcturon, enac, chlorfcnprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlomitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, hiamid, cinidon—ethyl, cinmethylin, cinosulfuron, cisanilide, Clcthodim, cliodinatc, clodinafop, clol’op, clomazonc, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, m bis(hydrogen methylarsonate) (CMA), copper sulfate, l—chloro—N9—(3,4— dichlorophenyl)—N—N—dimethylformamidine (CPMF), l—chloropropan—Z—yl N~(3— phenyl)carbamato (CPPC), crcdazine, crcsol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, ydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, lor, desmedipham, desmetryn, di—allate, dicamba, dichlobenil, dichloralurea, dichlormate, rprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, oquat, enican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, enamid—P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, 1001608519 dipropetryn, diquat, disul, dithiopyr, diuron, 2,2-bis(hydroxymethyl)propionic acid (DMPA), 2- —4,6-dinitrophenol (DNOC), dimercaptosuccinic acid , ethyl bis(2— ethylhexyl)phosphinate (EBEP), eglinazine, endothal, epronaz, S-ethyl dipropylthiocarbamate (EPTC), erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, mesate, fen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, lam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop—M, flazasulfuron, florasulam, fluazifop, fluazifop—P, fluazclate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, lluoronitrol’en, fluothiuron, l‘lupoxam, flupropacil, flupropanatc, flupyrsulfuron, fluridone, lluorochloridone, lluoroxypyr, llurtamone, lluthiacet, fomesafen, fbramsulfurcn, f‘osamine, furyloxyfen, glufosinate, glu‘fosinatc—P, glyphosate, halosafen, halosulfuron, dine, fop, haloxyfop-P, loroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethanc, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, iscxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lcnacil, linuron, mcthacrylic acid (MAA), ammonium hydrogen methylarsonate (MAMA), (4— Chloro—Z—methylphenoxy)acetic acid (MCPA), MCPA—thioethyl, 4«(4—Chlor0—2— methylphenoxy)butanoic acid (MCPB), mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, omuron, metolachlor, lam, metoxuron, metribuzin, metsulfuron, molinate, de, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, dium methyl arsenate (MSMA), naproanilide, napropamide, naptalam, neburon, lfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho—dichlorobenzene, orthosulfamuron, in, rgyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, rfen, parafluoron, paraquat, pebulate, pelargonic acid, ethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, 1001608519 phenmedipham—ethyl, phenobenzuron, mercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, achlor, primisulfuron, procyazine, mine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, uizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, ofop-P, rhodethanil, rimsulfuron, saflufenaeil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, styrene maleic anhydride (SMA), sodium arsenite, sodium azidc, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, cturon, sulfosulfuron, sulfuric acid, sulglycapin, swep, trichloroacetic acid (TCA), tebutam, tebuthiuron, ltrione, tembotrione, tcpraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluoron, thenylchlor, thiazallttoroni, thiazopyr, thidiazimin, thidiazuron, thiencarbazone—methyl, thifensulfiiron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri—allate, triasulfuron, flam, tribenuron, tricamba, triclopyr, tridiphane, trietazinc, trifloxysulfilron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, uron, tripropindan, tritac ulfuron, vernolatc, and xylachlor.

21. The composition of claim 13, wherein the concentration ofthe compound is from 0.1 to 1000 ppm.

22. The ition of claim 13, wherein the tration of the nd is from 1 to 500 ppm.

23. The method of claim 15, wherein the fungicidally effective amount is from 0.01 to 0.45 grams per square meter.

24. The compound of any one of claims 1 to 12, substantially as herein described.