NZ732495B - Fungicidal compositions - Google Patents

Abstract

Described herein are fungicidal compositions and methods of controlling fungal plant pathogens or diseases, employing a fungicidal composition comprising: a) a fungicidal compound of the Formula; a) at least one ionic surfactant; b) at least one nonionic surfactant; c) from about 50 g/L to about 700 g/L of benzyl acetate; and d) at least one N,N-dialkylcarboxamide; wherein the benzyl acetate and the at least one N,N-dialkylcarboxamide together form a water immiscible organic solvent. The compositions are homogeneous, stable upon storage, and upon dilution in water form stable emulsions that can be sprayed onto plants to control important fungal diseases. g/L of benzyl acetate; and d) at least one N,N-dialkylcarboxamide; wherein the benzyl acetate and the at least one N,N-dialkylcarboxamide together form a water immiscible organic solvent. The compositions are homogeneous, stable upon storage, and upon dilution in water form stable emulsions that can be sprayed onto plants to control important fungal diseases.

Description

lt‘lJNGlClDAL COMPGSYFEGNS PRlORlTY CLAlM This ation claims the benefit of US. Provisional Application No. 62/098,l99, filed December 30, 20H, US. Provisional Application No. 62/098,202, filed December 30, Uh 2014, and US. Provisional Application No. 62/098224, tiled December 30., 20%, the complete disclosures of all of which are hereby expressly incorporated by reference.

FEE-Ll} 0F THE ENVENTEON Sorne s of the invention relate to emulsions which include fungicides and are suitable for use in agriculture.

BACKGRGUNI) AND Still/EMARY Liquid pre—rriix concentrates comprising two or more active ingredients are useful in a Wide variety of agricultural applications. For example, two or more pesticidal active ingredients may be combined in order to control a wider spectrum of pests, or to utilize multiple modes of action, ed to the individual active ingredients alone.

Water insoluble pesticide active ingredients may be formulated in water as aqueous sion trates (SC) or by dissolving the water insoluble pesticide in an organic solvent and forming an ernulsiliable concentrate (EC). The preparation of these liquid, pre— niix trates can be challenging owing to chemical and/or physical ility issues. liahle concentrate formulations, also known as emulsion concentrates or ECs, are widely used in crop tion. The disadvantages of some ernulsifiahle concentrates include their poor cold temperature stability and the nced tendency of the active ingredient to cwstallizet owing to the low solubility of some active ingredients in the concentrate. it was an object of the present disclosure to provide an emulsifiable concentrate which overcomes these disadvantages.

Some aspects of the invention provide fungicidal compositions comprising: a fungi cidal compound ol‘the Formula: KJI at least one ionic surfactant; at least one nonionic surfactant; an acetate ester; and an N,N— lcarhoxaimde. in. certain embodiments, the described fungicidal composition may include at least one additional fungicidal compound.

In certain embodiments, the acetate ester and the N,N—dialkylcarhoxamide together form a water immiscible organic solvent for the described fungicidal ition, In certain ments, the described fungicidal composition forms a stable, hoinogenous emulsifiahle concentrate that readily fies and forms a stable emulsion without ciystallization of the fungicidal nd when added to water. in certain embodiments, the described composition may include an adjuvant that improves the fungicidal performance of the composition.

In certain embodiments, the described composition may include additional active ingredients and/or inert formulation ingredients.

Also ed herein is a method of controlling plant derived fungal pathogens or diseases comprising ting the vegetation or an area adjacent thereto to prevent the growth of the fungal pathogens or diseases with a fungi cidally ive amount of a fungicidal composition comprising: a fungicidal compound of the Formula: at least one ionic surfactant; at least one nonionie surfactant; an acetate ester; and an N,'N~ dialltyloarboxantide. ()1 A first set of embodiments ofthe present disclosure includes fungicidal compositions comprising: a) a fungicidal nd of the Formula b) at least one ionic surfactant; c) at least one nonionie surfactant; d) at least one acetate ester; and e) at least one N,N~diallwl.oarboxamiden A second set of embodiments includes the twigioidal compositions ofthe first set of embodiments, wherein the composition includes: H [.0 a) front about 1 gram per liter (g/L) to about 200 g/L of the fungicidal nd of the Formula b) from about i g/ a to about EGO git of the at least one ionic surfactant? wherein the at least one ionic surfactant includes at least one anionic surfactant; c) from about 1 g/L to about 200 g/L of the at toast one nonionic surfactant; (1) from about 50 g/L to about 700 g/L of the at least one acetate ester; and e) from about 25 g/L to about 300 g/L of the at least one NN—dialisyicarboxaniide, wherein the at ieast one N,N—dialkyicarboxaniide inctudes an N,N—diinethyi fatty acid amide.

A third set of ments ineiudes the fungicidal composition of any of the first and/or the second set of embodiments, n. the composition includes from about 1 gram per liter (fig/L) to about 200 g/L of the fungicidal compound of the Formula: A fourth set of embodiments includes the fungicidal composition of any of the first h the third set of embodiments, wherein the ition includes from about t g/I... to about 100 g/L of the at least one ionic surfactant, wherein the at toast one ionic surfactant inciudes at least one anionic sutftatctant.

A ti ttti set of embodiments includes the fungicidal ition ot‘any of the first through the fourth set of embodiments, wherein the composition includes from about 1 g/L to about 209 g/L of the at least one nonionic surfactant.

A sixth set of embodiments includes the fungicidal composition of any of the first through the fifth set of embodiments, wherein the compositi on includes from about 50 g/L to about 700 g/L of the at least one acetate ester.

A seventh set of embodiments includes the fungicidal composition of any of the first [A through the sixth set of embodiments, n the composition includes from about 25 g/L to about 300 g/L of the at least one N,N~dialkylcarboxamide, wherein. the at least one N,N- diallcylcarboxamide includes at least one of an N,N—dimethyl fatty acid amide.

An eighth set of embodiments includes the fungicidal composition of any of the first through the seventh set of embodiments, wherein the at least one acetate ester and the at l. 0 least one N,N~dialkylcarhoxamide together form a water immiscible organic solvent, A ninth set of embodiments includes the fungicidal composition of any of the first through the eighth set of embodiments, wherein the weight ratio of the at least one acetate ester : the at least one alkylcarhoxarnide ranges from about l-l O : 1—10, A tenth set of embodiments includes the fungicidal composition of any of the first )n-nl KJI through the ninth set of embodiments, wherein the weight ratio of the at least one acetate ester : the at least one itilhylcarboxamide ranges from about l—S : l-2.

An eleventh set of embodiments includes the fungicidal composition of any of the first through the tenth set of embodiments, wherein the at least one acetate ester is selected from a group consisting of benzyl acetate, exylrnethyl e and phenyl acetate.

A twelfth set of embodiments includes the fungicidal composition of any of the tirst through the th set of ments, wherein the at least one N,N—dialkylcarboxamide is selected from a group ting of N,N—diinethylhexanamide, N,deimethyloctanamide, N,N~dimethyldecananride and N,N-dirnethyldodecanamide.

A thirteenth set of embodiments includes the fungicidal composition of any of the first through the twelfth set of embodiments, further including at least one additional idal compound.

A fourteenth set of embodiments includes the idal composition of the thirteenth set of embodiments, wherein the at least one additional fungicidal compound is selected from a group consisting of azoxystrobin, bifuituizhi, cournethoxystrohin, coumoxystrobin, dimoxystrobin, enestroburin, enoxastrohin, nstrobin, fei'iosystrobin, llut‘enoxystrobin, strohin, jiaxiangjunzhi, kresoxim—methyl, ntandestrobin, nietoininostrobin, orysastrobin, picoxystrobin, pyraclostrobin, tostrobin, pyraoxystro'bin, triclopyricarb, trifloxystrohin, methyl 2»{2—(2,5—dirnethylphenyloxymethyl)phenyl lu3 —methoxyacrylate, azaconazole, bitertanol, bromuconazole, cyproeonazole, ditenoconazole, diniconazole, diniconazole—h/l, epoxiconazole, lenhuconazole, tlnquinconazole, llnsilazole, tlutriafol, hexaconazole, imibenconazole, ipconazole, rnetconazole, myclohutanih oxpoconazole, paclohu‘trazole, penconazole, pi'opiconazolei prothioconazole, simeconazole, tehnconazole, tetraconazole, triadimefon, triadimenol, triticonazole, nniconazole, imazalil, pefurazoate, [A prochloraz, triflnmizole, pyrimidines, fenarimola nuarimol, pyrifenoxa and triforine.

A fifteenth set of embodiments includes the fungicidal composition of the thirteenth and/or the fourteenth embodiments, wherein the at least one additional fungicidal compound is selected from a group consisting of azoxy strobin, kresoximsinethyl, picoxystrobin, pyraclostrohirg trilloxystrohina epoxiconazole, fenhoconazolej utanil, propiconazole, l. 0 prcthioconazole and tehuconazole.

A sixteenth set of embodiments es the fungicidal composition of any one of thirteenth through the fifteenth set of embodiments} wherein the at least one additional idal compound is selected from a group ting clostrohin, prothioconasole and onazole. kit A seventeenth set of embodiments includes the idal composition of any of the first through the sixteenth set of ments? further including an adjuvant that improves the fungicidal performance of the composition selected from a group consisting of a non— ionic surfactant, a polyether modified opolysiloxane and an alltyl phosphonate.

An eighteenth set of emhodiments includes s of controlling fungal plant 2.0 pathogens or diseases comprising the steps of contacting the vegetation or an area adjacent thereto to prevent the growth of the fungal pathogens or diseases with a, t‘nngicidally effective amount of a fungicidal composition comprising: a) a fungicidal nd of the Formula //""" ix) [J] h) at least one ionic surfactant; c) at least one nonionic surfactant; d) at least one acetate ester; and e) at least one N,N—dialkylcarboxamide A nineteenth set of embodiments includes the methods of the eighteenth set of embodiments, wherein the fungicidal composition includes from about i gram per liter (g/L) to about 2th) g/L of the fungicidal compound of the Formula A eth set of embodiments includes the methods of the eighteenth and/or the nineteenth set of embodiments, wherein the idal ition includes from about 1 g/l; to about too g/L- of an anionic surfactant of the at least one ionic surfactant, wherein the at east one ionic surfactant includes at least one anionic surfactant.

A twenty first set of embodiments includes the methods of any of the eighteenth through the twentieth set of embodiments, wherein the fungicidal ition includes from about l g/L to about 200 g/L of the at least one nonionic sui'tactant.

A twenty second set of embodiments includes the methods of any of the eighteenth h the twenty first set of embodiments, wherein the fungicidal. composition includes from about 50 g/L- to about 700 g/L of the acetate ester.

A twenty third set of embodiments includes. the methods ofany of the eighteenth through the twenty second set of ments, wherein the idal composition includes from about 25 g/L to about 300 g/l; of the at least one N,N~diallgylcarboxamide wherein the at least one N,N—dialltylcarhoxamide includes an N,N~dimethyl fatty acid amide.

A twenty fourth set of ments includes the method of any of the eighteenth through the twenty third set of embodimenta wherein the at least one acetate ester and the at least one NtN—diallrylcarboxaniide together form a water immiscible organic solvent A twenty fifth set of embodiments includes the methods of any of the eighteenth through the twenty fourth set of ments, wherein the weight ratio of the at least one acetate ester : the at least one N,N~diall<ylcarhr_ixamide ranges from about 140 : l-l t‘i.

WO 09634 2015/068011 A twenty sixth set ofemhodiments includes the methods ofany ot‘ the eighteenth through the twenty fifth set of embodiments, wherein the weight ratio of the at least one acetate ester : the NiN—dialkylcarboxamide ranges from about l—S : 1—2.

A twenty seventh set of ments includes the s of any of the eighteenth VJ] through the twenty sixth set of embodiments, wherein the at least one acetate ester is selected from a group consisting of henzyl acetate, cyclohexylrnethyl acetate and phenyl acetate.

A twenty eighth set of embodiments includes the methods of any of the enth through the twenty h set of embodiments, wherein the at least one NM“ dialkylearhoxamide is selected from a group consisting of N,N-diinethylhexanarmde, N,N- dimethyloctanamide, NN—dimethyldecanamide and MN—dimethyldodecanamide.

A twenty ninth set of embodiments includes the methods of any of the eighteenth through the twenty eighth set of embodiments, n the water immiscible organic solvent includes henzyl acetate and one or more than one of a fatty acid N,N—diallx:ylcarhoxamide.

A thirtieth set of ments includes the methods of any of the eighteenth through the twenty ninth set of embodiments, the fungicidal composition further comprising at least one additional fungicidal compound A thirty first set of embodiments includes the methods of any of the thirtieth set of embodiments, wherein the at least one additional, fungicidal compound is ed from a group consisting of azoxystrohin, hifniunzhi, couniethoxystrohin, ystrohin dimosystrobin, enestroburin, enoxastrohin, fenarninstrohin, fenoxystrohin, Elufenoxystrohin, fluoxastrohin, jiaxiangjnnzhi, hresoxinivmethyl, mandestrohin, metominostrobin, eiysastrobin, picoxystrohin, pyraclostrobin, pyrametostrobin, ystrobin, trielopyricarh, tritloxystrohin, methyl 2~[242,5~dimethylphenyloxymethprhenyl}~3~rnethoxyacrylate, azaoonazole, hitertanol, bromuconaxole, cyproconazole, ditenoconazole, diniconazole, $3\ diniconazole~M, epoxieonazole, fenhueonazole, tluquineonazole, flusilazole, llutnafol, hexaconazole, iniihenconazole, ipconazole, azole, utanil, oxpoconazole, paclohutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tehuconazole, tetraconazole, mefon, triadimenol, triticonazole, uniconazole, imazalil, pefurazoate, pi'ochloraz, tritiumizole, pyrimidines, fenarimol, nuarimol, pyrifenox, and triforine.

WO 09634 A thirty second set of embodiments includes the methods of any of the thirtieth through the thirty first set of embodiments, wherein the at least one additional fungicidal compound is selected. from a group consisting of azoxystrobin, liresoxim—methyl, picoxystrobin, ostrobin, ti'itloxystrobin, epoxiconazole, fenbuconazole, utanil, [J] propiconazole, prothioconazole, and tehuconazole.

A thirty third set of embodiments includes the methods of any of the thirtieth through the thirty second set of embodiments, wherein the at least one additional fungicidal compound is ed from a group consisting of pyraclosti‘ohin, prothioconazole and propieonazole. l O A thirty fourth set of embodiments includes the methods of any of the eighteenth through the thirty third set of embodiments, the fungicidal composition further comprising an adjuvant that improves the fungicidal performance of the fungicidal composition selected from a group consisting of a non—ionic tant, a poly ether modified organopolysiloxane and an alkyl phosphonate, ./ A thirty fifth set of embodiments includes the methods of any of the eighteenth through the thirty fourth set of embodiments, wherein the fungal plant ens include Septorz'a i, Punching triticii'za, il/Zycosphaereli'a icola, Puccinia trit‘cma, Puccinia Striifiirmz‘s, Vending Masque/Us, Ustilago maydzis, (/ltciitultntecamr, Rhynchospormm secaz’z's, Leptospitaerm itodorum, ftvt'agnaporthe grisea, ill/{ordinateflucn‘eola. qneronospora cubensz's, PSeudocercosporeila herpoz‘richoz'des, Phakopsom lDtZC/I’Ij/Wlll'Zl, Pizaeosphaeria nodorum, Biumeria grnminis trzlici, Binmerz'n gmmims horit'ei, Erysz'phe Czchomceamm, Ezysip/"ze groomer/it’s, (Homerelk [tigennritmt Cercospora helicoi’a, Afterward: salami, Rhizoctonm salami, Plczsn'zopara viiicola, Phytophiharcz Milestone Pyriculnria or nae, and phora teres, b.) {J} A thirty sixth set of embodiments es the methods of any of the eighteenth through the thirty fifth set of embodiments, wherein the fungal plant diseases include antl'iracnose, blasts, hotrytis, brown inst, hlis‘ter smut, brown rot, downy mildew, fosarium, powdery mildew, rusts, gliime blotch, leaf , net blotch, sheath blight, stripe rust, scab, eye snot, leafspot, early blight, and late .

A thirty seventh set of embodiments includes the compositions or methods of any of the eighteenth through the tl'iirty sixth set of embodiments, wherein the at least one ionic 2015/068011 surfactant is an anionic surfactant selected from a group consisting of an alkali, alkaline earth and ammonium salt of an alkylarylsulfonic acitl A thirty eighth set of embodiments includes the compositions or s ol‘any of the eighteenth h the thirty seventh set of embodiments, wherein the at least one [J] nonioriic surfactant is ed from a group consisting ol’an alcohol initiated ElO/PO block copolymer and an alcohol etl'ioxyla‘tel A thitty ninth set ol’ embodiments includes idal compositions comprising: a) a fungicidal compound of the a b) a calcium salt of an alkylaiyl sulfonate; c) an alcohol initiated EO/PO block copolymer; d) a tridecyl alcohol ethoxylate; e) a poly ether modified organopolysiloxane; l’) lienzyl acetate; and g) an N,N-<limethyl fatty acid amide.

A fortietli set of embodiments includes fungicidal compositions comprising: a} a fungicidal compound ofthe Formula proihioeonazole; a calcium salt of an alkylaiyl sulfonate; an alcohol initialed EO/FO block copolymei'; a ‘lrideeyl alcohol late; a polye’ilier modified. organopolysiloxane; henzyl acetate; and an N9N~dimelliyl fatty acid amide.

A forty first set of embodiments es fungicidal compositions comprising: a) a fwiglcidal compoxmd of the Formula \‘3 O C3"” Q \ N! i .

N ll pyraclostrobin; an calcium salt of an alkylaryl sulfonale; an alcohol led Fifi/PO block copolymer; a tiidecyl alcohol etlioxylate; a poly either modified organopolysiloxane; -11“ 2015/068011 g) henzyl acetate; and h) an. N',N —dimetliyl fatty acid amide DETAELED DESCREPTEGN Some aspects of the invention described herein include fungicidal compositions in the form of an eniulsil’iable concentrate (ie, an on concentrate or EC) that includes at least one fungicidal compound, two or more surfactants and. a water ible c solvent comprised of a mixture of organic compounds including an acetate ester, an NN— dialkylcarhoxamide and optionally, at least one of a itetone and an alcohol. The described fungicidal composition exhibits good storage stability and readily forms a stable, l O homogenous emulsion upon dilution into a spray solution of water. The described fungicidal ition ts protectant and curative control of the important fungal diseases Septoria tritici (wheat leaf blotch) and ia triticina (wheat brown inst) when utilized in spray applications.

Unless specifically or implicitly stated otherwise the term 'ahout‘ as used herein y—d KJI means plus or minus 10 percent. For example, ’about ll)“ encompasses the range ofllfl to One exemplary embodiment provided herein is a idal composition comprising: a. a fungicidal compound of the Formula h. at least one ionic surfactant; f: at least one nonionic surfactant; d. an acetate ester; and n: an NN—dialkyl carboxainide.

A. First Fungicidal Compound -ias.'.« fine of the fungicidal compositions described herein is comprised ot‘a first fungicidai compound of the Forniuia. which is a chemical derivative of the natural t UKeZA as described in US. 6,861,390 (the disclosure of which is hereby incorporated by reference in its entirety), and has the Chemical Abstracts (CAS) Number 517875-344 and the CAS name: propanoic acid, :2- n, {Elimmethoxynzn { [{(3 S,’7R,8R,9S)—9—methyi~8—(2—n1ethybi~oxopropoxy)—2,6—dioxo—7— (phenylmethyi)~1,S-dioxonan—S-yiiamino’icarbonyi}-3—pyridinyii§oxyilinethyi ester. The first fungicidal compound ts bioiogioai controi of certain fungat diseases such as for i, 0 example, Septoita tritici ‘R; wheat teat" blotch) and ia triticiria 'I‘; wheat brown rust). The first fungicidal compound wiii be referred to herein as Compound A.

In some embodiments the fungicidai compositions described herein may comprise, with respect to the compoin ti on? from about 1 gram of active ingredient per titer (g ai/L) to about 200 g ai/L, from about 5 g ai/L to about 175 g ai/L, from about 10 g ai/L to about 150 —4 KJI g ai/L, from about 20 g ail/L to about 125 g ai/L, from about 20 g ai/L to about 100 g ai/L, from about 20 g ai/L to about 90 g ai/L, from about 30 g air/L to about 90 g ai/L, from about 40 g ai/L to about 90 g ai/L, from about 40 g ai/L to about 80 g ai/L, from about 45 g ai/L to about '75 g ai/L, or from about 50 g ai/L to about 70 g ai/L of Compound A. The tungicidal compositions described herein may aiso comprise, with respect to the composition, from to.1.“ about 30 g ai/L to about 1:30 g ai/L, from about 40 g ai/L to about 3:30 g ai/t from about 50 g ai/L to about 150 g ai/L, from about 60 g ai/L to about 150 g ai/L, from about 70 g ai/L to about 150 g ai/L, from about 80 g ai/L to about 150 g ai/L, from about 90 g ai/L to about 150 g ai/L, from about 100 g ail/L to about 150 g ai/L, from about 125 g ai/L to about 150 g ai/L, from, about 50 g ai/L to about 14-0 g. aids, from about 50 g ai/L to about tSO g ai/L, from about 50 g ai/L to about 120 g ai/L, from about 50 g ai/L to about 110 g ai/L, from about 50 g 2015/068011 ai/L to about lilo g ai/L, from about 50 g ai/L to about 90 g ai/L, or from about 50 g ai/L to about 80 g ai/L of Compound AV E. Surfactants 'l'he fungicidal composition described. herein may e more than one surfactant [‘1] which may e one or more than one each of an ionic and a non—ionic tant. Such surfactants may be used as an emusitier, dispersant, sol er, wetter, ant, protective colloid, or for other purposes. Examples of surfactants are listed in McCutcheonln Vol. l: Eniulsifiers a Detergents, McCutcheon‘s Directories, Glen Rock, USA, 2008 (lnternational Ed. or North American Ed). Since the described fungicidal composition is an emulsitiahle concentrate (EC), surfactants are used to emulsify the EC when it is added to spray water so it forms a stable and homogeneous emulsion that can be readily applied by spray application to control target pests. le ionic surfactants for use with the fungicidal composition described herein may include anionic suifactants such as alkali“, ne earth or ammonium salts of p—d {)1 sulfonates, sulfates, phosphates, carboxylates, and mixtures f. Examples of sulfonates are alhylaiylsulfonates, diphenylsulfonates, alpha—olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl— and tridecylbenzenes, sul ‘onates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethosylated alkylphenols, of alcohols, ofethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carbonylated alcohol or alkylpheiiol ethoxylates. Preferred anionic surfactants are sulfates and. a‘tes. in some ments the ionic surfactant for use with the fungicidal composition described herein may include an c surfactant such as an alkali, alkaline earth or ammonium salt of an alkylarylsulfonic acid such as sulfonate salts of dodecylu and/or tridecylbenzenes, sulfonate salts of naphthalenes and/or alkylnapltthalenes, and salts of sulfosuccinates and/or sulfosuccinamates. ln some embodiments the ionic surfactant is an alkaline earth salt of an alkylaryl sulfonate. In some ments the ionic surfactant is calcium dodecylbenzene sullonate which is available as Némsa® EVM 70/2E from l-luntsman littemational LLC ('l‘he Woodlands, TX), In some embodiments the fungicidal composition described herein may comprise, with respect to the composition, from about i grain per liter (g/L) to about l 00 g/L, from about 5 g/I to about lttl) g/l from about It) g/L to about 100 g/Is, from about 20 g/L to about ltIU g/L, from about 30 g/L to about 100 g/L, from about 30 g/L to about 90 g/,L from about [A 30 g/L to about 80 g/L, from about 40 g/L to about 70 g/L, from about 50 g/L to about ’70 g/l, or from. about 55 g/I to about 65 g/L of at least one of an ionic surfactant.

In some embodiments, the idal composition described herein may include a surfactant that is a ic surfactant. Suitable nonionic surfactants for use with the fungicidal compositions described herein may include all<oxylates, ituted fatty acid l. O amides, amine oxides, esters, sugar—based tants, polymeric surfactants, and mixtures thereof. Examples of allroxylates are compounds such as alcohols, alkylplienols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkonylated with from 1 to 50 molar lents of an alkoxylating agent such as ethylene oxide IEO) and/or ene oxide (PO).

»-—A kit In some embodiments the fungicidal composition described herein may include a nonionic surfactant that is an alkoxylate such as, for example, an alcohol initiated EO/PO block copolyrner such as a butanol initiated ELI/PO block copolymer, which may also be lmown as a polyalkylene glycol monobutyl ether, a poly<ethylene glycol—co-propylene glycol) monobutyl ether, or a propylene oxide ethylene oxide polymer nionobutyl ether. In to4.1, some embodiments the bu‘tanol initiated EQ/I’O block copolyiner may have a degree of ethoxylation of from about 20 to about 30 and a degree of propoxylation of from. about 20 to about 30. Suitable examples of these EG/PO block copolymers may include ”l‘oxiniulde) 8320 available from Stepan (Northtield, IL), Terrnulfi?) 5429 available from Huntsman International LLC (The Woodlands, 'l‘X), 'I'ergitolTM Xi) available from Dow Chemical (Midland, MI), and Ethylanm NS SOOLQ available from AkzoNobel (Chicago, IL).

In some ments the fungicidal ition described herein may include a nonionic surfactant that is an alkoxylate such as, for example, an l initiated ISO/PO block, copolymer like a xy—l-butanol ted ISO/I’D block, copolymer (CAS number 99821—019) of which ‘M (36000 and AtlasTM GS OO’ZL are examples, and which are available from Croda (Edison, NJ). In some embodiments the 4—butoxy—I—butanol initiated PLO/PO block, copolymer may have a degree of ethoxylation of from about 20 to about 30 and a degree of propoxylation of from about 20 to about 30. in some embodiments the nonionic tant for use with the tungicidal composition described herein that is an alcohol initiated FLO/PO bl ock copolymer may provide improved active ingredient stability to the ition.

In some embodiments the fungicidal composition described herein may include a [A nonionic surfactant that is an alcohol ethoxylate such as a tridecyl l ethoxylate; of which i~1;v'ri.pei.‘r_inicTM til/l 0, available from Croda (Edison, NJ), is a suitable example which es l0 E0 units e of etboxylation of 10) in some embodiments the fungicidal composition described herein may include surfactants selected from the group consisting of at least one ionic surfactant that is an l. O anionic surfactant and at least two non~ionic surfactants.

In some embodiments the fungicidal ition described herein may comprise, with respect to the composition, from about 1 gram per liter (g/L) to about 200 g/L from about l0 g/L to about l90 g”L from about l0 g/L to about l80 gfL, from about 20 gl to about 160 g/L, from about 30 g/L to about l50 g/L, from about 40 g/L to about 140 g/Ls from »-—A kit about 50 g/L to about l30 g/L, from about {—30 g/L to about 120 g/L, from about 70 g/L to about ll0 g/L, from about 80 g/L to about l00 g/I, or from about 85 g/L to about 95 g/L of at least one of a non-ionic surfactant, (3. Water ihle Organic Solvent In certain embodiments, the described fungicidal ition includes a water immiscible organic solvent. “Water immiscible organic t” as defined herein means an organic solvent that has low water solubility and when mixed with an equivalent volume of water forms two discrete liquid layers. In some embodiments, the described fungicidal composition includes a water immiscible organic solvent that has a solubility in water of not greater than about 500 rug/L, about 600 trig/L, about 700 rug/L, about 800 tug/L, about 900 mg/L, or about 1000 tug/L. in some embodiments, the described, composition includes a. water immiscible organic solvent that has solubility in water of not greater than about 1250 mg/L, about 1500 rug/L, about l750 mg/L, about 2000 rug/L, about 3000 mg/L, about 5000 rug/L, about 10,000 trig/L, about 20,000 trig/L, about 30,000 trig/L, about 40,000 rug/L, or about 50,000 mg/L.

In some embodiments; the water immiscible c solvent serves as a liquid medium that dissolves the active and inert ingredients of the described fungicidal composition to form a stable solution (ides an emulsifiable concentrate) that forms a stable emulsion when added to water. vl6~ in some embodiments, the water immiscible organic solvent is comprised of a mixture of at least three organic compounds or classes of organic compounds. These organic compounds may be selected from the chemical s of ester compounds, amide compounds, ltetone compounds, and alcohol nds. The organic compounds that make [A up the water immiscible organic solvent mar)1 be derived from natural sources such as vegetable, seed or animal oils, and/or from petrochemical sources. in some embodiments, the fungicidal composition described herein includes a water immiscible organic solvent comprising of a mixture of organic compounds including at least one each of: an acetate ester, an N,N~dialltylcarboxamide, and at least one of a lretone and an l. O alcohol, in some embodiments, the fungicidal composition described herein includes a water immiscible organic solvent comprising ofa e of organic compounds including at least one each of: an acetate ester and an N,N~dialltylcarboxamide.

Suitable organic compounds that may comprise the water immiscible organic solvent y—A kit of the fungicidal composition described herein that are acetate esters may include compounds such as, for example, n~butyl acetate, iso—butyl acetate, n—pentyl acetate, ntyl acetate, n- hexyl e, iso-bexyl e, exyl acetate, phenyl acetate, yl acetate, iso— heptyl acetate, cyciohexylmethyl acetate, benzyl e, or mixtures f. Benzyl acetate is available as lefthol l5 from Huntsman (The Woodlands, TX). to44‘ In some embodiments, the described fungicidal composition may include, with respect to the composition, from about 50 g/.l to about 700 g/L, from about lt‘u’) g/l to about 700 g/L, from about 150 g/L to about 700 g/,L from about 200 g/L to about 7tlt‘; g/L, from about 250 g/L to about 700 g/,L from about 275 gz’L to about 650 g/L, from about 300 g/L to about 6th , from about 3.50 g/L to about 550 g,1’l_,, from about 375 g/L to about 550 g/L, from about 3.75 g/L to about 500 g’L, or from about 400 g/L to about 475 g/L of an e ester.

In some embodiments, suitable organic compounds that may comprise the water immiscible organic solvent of the described fungicidal composition may include benzyl acetate, cyclohexylmethyl acetate, phenyl acetate, or mixtures thereof, ln some ments, suitable organic compounds that may comprise the water immiscible organic solvent of the described fungicidal composition may include benzyl acetate.

Suitable organic compounds that may comprise the water immiscible organic solvent of the fttngicidal composition described herein that are N,N-diall<ylcarboxantides include the -17s naturally derived fatty acid diniethylaniides such as, ag, N,N—dimethylcaprylamide (MN— dimethyloctanamide), N,N—dinietliylcapramlde (N,N—iliitietliyldecanamide), and mixtures thereof, which may also be known as the NN—dimethyl fatty acid amides and are available commercially as Agnique® Alli/ll) 810 and e® AMD 10, from BASF Corp, (Florliai’n [A Paris, NJ}, Genegen® 4l66, Genegen® 423l and Genege ® 4296, from Clariant (Charlotte, NC), Hallconiid M—S—lt) and mid MwlO, from Stepan (Noithlleldi 1L), and Armid Elli/lit) and Aer DM8l0 from AlizoNobel (Chicago, 1L). These ts may also include small s of methylhexanamide and/oi N,N-dimethyldodecanainide. Additional examples ot‘i'iaturally derived organic compounds that are N,N~dialkylcarboxamides include l. O the morpholine amides of caprylic / captic fatty acids (Cg/Cm) which are commercially ble as L® AGnl73U Solvent from Huntsman international LLC (The Woodlands, TX). in some embodiments, the described fungicidal ition may e, with respect to the composition, from about 25 g/L to about 300 g/L, from about 25 g/L to about y—i KJI 300 g/L, from about 50 g/L to about 300 gal, from about 75 g/L to about 300 g/L, from about lOO g1 to about 300 g/L, from about 125 g/L to about 300 g/L, from about lSO g/L to about 300 g/L: from about l75 g/L to about 3.00 g/L, from about l75 g/L to about 250 31/1,, from about l'75 g/L to about 200 g/L, from about 200 g/L to about 250 g/L, from about 225 g/L to about 300 g/L, from about 250 g/L to about 300 g’L, or from about 270 g/L to about 300 g/L so44‘ of at least one N,N—dialltylcai'boxamide, in some embodiments, the described fungicidal composition may include one or more than one aN,Nndiall<ylcarboxaniide selected from the group consisting of N,Nn dimethylcapiylamide, N,N~dimetliylcapramido, or mixtures thereof. in some ments, suitable organic compounds that may comprise the water immiscible organic solvent of the fungicidal composition described herein that are at least one of a ketone and an alcohol may include compounds such as, acetophenone, cyclohexanone, ethyl isopropyl ketone, Z-lieptanone, 2-l'iexanoi'ie, isophorone, methyl isobutyl ketone, 3~methyl-2vpentanone, Zmpentanone, 3mpentanone, trimethylcyclohexanone (dihydroisophotone), cyclohexanol, Zuheptanol, Znethylhexanol, and straight chain alcohols such as, for example, l~hexanol, 1— anol, l-octanol, l—nonanol, l~decanol, and the like, fatty alcohols such as oleyl alcohol and the like, and mixtures thereof.

In some embodiments, the bed fungicidal composition may include, with respect to the composition, from about 25 g/L to about l50 g/,L from about 50 g/L to about 150 g/L, from about 50 g/L to about l25 g/L, from about 60 g/L to about 120 g/L, from about ’70 g/L to about lZG g/L, from about 70 53/32 to about 1 l0 g/L, from about 70 g/L to about 1% g/L, or from about 7'0 g/L to about '90 g/L, of at least one of a, ketone and an alcohol. in some embodiments, the at least one of a ketone and an alcohol included in the described fungicidal composition may be selected from the group consisting of acetophenone, [A cycloliexanone, Znethylhexanol, Zuheptanol, and es f. lnmmmemhflmwmadwaflmoumemekmmwamhmakdwlmdwhdmdm described fungicidal composition may be ed from the group consisting of acetophenone, cyclohexanone,and.unxturesthereo£ lnsmneenmodhnmnatheaflemdoneoiakmoneandanahmhdindudednidm l. O described, fungicidal ition may be cyclohexanone. in some embodiments, the at least one of a ketone and an alcohol included in the described fungicidal composition may provide improved solubility of Compound A in the described timgicidal composition. in some embodiments, the at least one of a ketone and an l included in the y—A KJI described fungicidal composition that is cyclohexanone, may provide improved lity of Compound A in the described fungicidal composition lnsmneenmomnmnwjheuemrumnmmbmommnmgohennnmimovfleunmmedml beneficial or synergistic s to the described fungicidal ition such as, for example: (1) improved fungicidal performance of the composition when applied in spray applications ”to44‘ to plants, (2) improved active ingredient solubility in the described compositions, and/or (3) improved Compound A. chemical stability in the described ition during storage. in some ments, the water immiscible organic solvent of the described fimgmdmcmmmnnmnmwpnwfleummmmmdbmmfimdorgmmpfihcdfidsnfltmflw formation of a stable, enous emulsili able concentrate that readily emulsilies and forms a stable, oil—in-water emulsion without iable crystallization or itation of any of the ingredients when the composition is added to water, msomemnhflhmmmgme“amtnmnmeeoomnmsohmnofmefimgmmm compositions described herein may include benzyl acetate, one or more than one of a fatty acid N,N~dimethylcarboaamide and cyclohesanone. hnmnwenmomnwnmfihewamrnmnmdmeoomnmSManofMefimgon compositions described herein may include benzyl acetate and one or more than one of a fatty acid N,N—dimethylearboxamide.

The water immiscible organic solvent that may provide the unexpected beneficial or synergistic effects to the fungicidal composition described herein may depend on the .19s selection of and]or the relative ratios of the organic compounds that comprise the water immiscible organic t. in some embodiments, the ratio of the organic compounds included in the water immiscible organic solvent of the idal composition described herein may range, on a [A weight basis, from about l—lO : l—lO : 1—10 of the e ester : the one or more than one of the fatty acid N,N—dimethylcarboxamide : the at least one of a ketone and an l. in some embodiments, the ratio of the organic compounds may range from about 1—8 : l—S : 1—5, from about 1—6 : 1—3 : 1—2., from about 2—6 : 1—3 : 1—2, from about 3—6 : 1—3 : 1—2, from about 4—6 : 1—3 : 1—2, from about 4—5 : ”id—2.5 : (id—l5, or from about 4.5—5 : lit-2.2 : 0.8—1.2 ofthe l. O acetate ester : the one or more than one of the fatty acid. NJN—dimethylcarboxamide : the at east one of a ketone and an alcohol, on a weight basis.

In some embodiments, the ratio of the organic compounds included in the water immiscible organic solvent of the fungicidal composition bed herein may range, on a weight basis, from about 4—6 : l—3 : 1—2, from about 4—5 : l.5—2.5 : 0.7—1.2, or from about 4.5- y—A kit 5 : 1.9—2.3 : ().8—l.l, of benzyl acetate : the one or more than one of a fatty acid N,N— dimethylcarbosami de : cyclohexanone. in some embodiments, the ratio of the organic compounds included in the water immiscible c solvent of the fungicidal composition described herein may range, on a weight basis, from about l-l 0 : l—lO of the acetate ester : the one or more than one of the to44‘ fatty acid N,N—diniethylcarboxamide, in some embodiments, the ratio of the organic compounds in the water immiscible organic solvent may range from about 1—5 : l—S, from about 1—5 : 1—2, from about l—4 : 1—2, from about 1—3 : l—Z, from about 1—3 : 1, from about 4 : i, from about 3 : i, from about 2 : l, or from about i : l of bei'izyl acetate : the one or more than one of a fatty acid N,N~dimethylcarboxamide.

In some embodiments, the described idal composition exhibits beneficial or synergistic properties related to the composition of the water immiscible organic solvent such as improved fungicidal efficacy after spray ation of the composition to vegetation or an area. adjacent thereto to prevent the growth of fungal ens or diseases. in some embodiments, the escribed fungicidal composition exhibits beneficial or synergistic properties related to the composition of the water immiscible organic solvent such as improved fungicidal l of Septoria tritici R; wheat leaf blotch) and Puccinia triticina (l’UCCR’l‘; wheat brown rust) after spray application of the composition to vegetation or an area adjacent thereto to prevent the growth of the fungal pathogens or diseases, in some embodiments, the escribed fungicidal composition exhibits beneficial or synergistic properties d to the composition ot‘the water immiscible organic t such as improved active ingredient chemical ity dining e In some embodiments, the described fungicidal ition exhibits beneficial or [A synergistic pi'opetties related to the composition of the water immiscible organic solvent such as improved, active ingredient lity in the composition.

E). Additional Fungicidal Compound in certain ments, the described fungicidal composition may include at least one additional fungicidal nd. Suitable at least one additional fungicidal compounds may include, for example, azoxystrohin, liifiiitinzhi, coumethoxystrol‘iin, counioxystrohin, dimoxystrobinj enestroburin, enoxasti‘obin, aininstrobin, fenoxystrobin, 'lliii’enoxystrohin, fluoxasti'obin, jiaxiangjunzhi, kresoxiin~methyL mandesti'ohin, metoniinostrobin, orysasti‘obin, picoxysti'obin, pyraclostiobin, pyrainetosttobin, ysti'obin, ti‘iclopyiicatb, ti'iiloxysti'obin, methyl 2—[2—(25dimethylplienyloxyme‘thyUplienyl}~3~nietlioxyacrylate9 pyrihen carbi triclopyiicarbil’clilorodincai‘h, famoxadon, fenaniidon, cyazofamid, aniisulbioni, benodanil, n, boscalid, cai'hoxin, fenfuram, fluopyiain, flutolanil, fluxapyroxad, etpyr, isopyrazani, inepi'onil, oxy cai'bosin, penlliit‘en, pentltiopyracl, sedaxane, tcclol‘talain, tliitl uzaniide, N-(4‘—tiilluorornethylthio- bipl'ienyl-iZ—yll—S —dilliiorometliyl—l— —lH~pyrazole~4~carboxannde, N—(Z—(l ,33— tritnetliylbutyl)plieiiyl)-l ,3~<limethyl~5~ fluoro—l H—pyi‘azole—4—caiboxaiiiide, N-[9~ (dichloromethylene)—l,2,3,4-tetrahydro—l,4— metltanonapltthalenuSuyl]—3—(diiluotomethyl)_l — metliylul H—py razole4—carhoxamide, dillutnetoriin binapacrylt dinobuton, dinocap, meptyl—dinocap fluazinamt feiimzone, anietcctradin, silthiofam, azaconazole, biteitanol, 'bioinuconazole, cyptoconazole, ditenoconazole, diniconazole, diniconazoleuM, epoxiconazole; fenhuconazole, lluquinconazole, lliisilazole, llutriat‘olj onazole, itnihenconazolea ipconazole, azole, hiitanil, nazole, paclobutrazole, pencenazole, propiconazole pi'otliioconazole, siineconazole, tehuconazole, tetraconazole, tnadimefon, ti'iadiinenol, triticonazole, uniconazole, imazalil, pet‘iirazoate, loraz, ti'illuniizole, pyrimidines, fenatinioli nuarimol, pyrifenox, tritbiiiie= aldiniorph, dodemorph, dodetnorpli acetate, fenpi'opimoi'pli, tridemorph, fenpiopidin, pipetalin, spii'oxaniine, fenhexamid, benalaxyl, benalaxyl—M, kiralaxyl, metalaxyl, metalaxyl—M (mefenoxam), ofut‘ace, oxadixyl, hyinesazole; octhilinone, oxolinic acid? bupirin'iate, benoinyh carbeiidaziin, falteridazole, WO 09634 thiabendazole, thiophenate-methyl, 5~chloro~’7_(4—methyl~ pipeiidin—l—yl)—6~(254,6— trilluoroplienyl)—[l ,2,4}ti‘iazolo{l ,S-elpytimidine, dietliol’eneai'b, etheboxam, pencyenron, fluopieolid, zoxamid, metrafenon, pyriofenoni cypmdinil, mepanipyiim, pyrimetlmnil, fluoroimjde, ipi‘odione, procynndone, Vinclozolin, fenpiclonil, fludioxonil, quinoxyfen, [A edifenphos, ipiobeiitos, pyrazophos, isoprothiolane, dieloran, quintozene, tecnezene, tolclofos—methyL yl, clilomneb, etridiazole, dimethomorph, flumorph, mandipmpamid, pyrimorpli, avalicarh alicai"b, valifenelate and 4-flum‘ophenyl N-(l —(l "(4" cyanophenylkthanesulfonyljtbut~2-yl)eaibamate, propamoearb, propamocarb hydrochloride, fer‘oam, maneozeb? mimeb, i'netirem, propine‘m tliiram, zineh. ziram, anilazine, ohlorotl’ialonil, l. O eaptafol, oaptan, felpet, diclilofluanid, dichlorophen, flusulfamide, hexachlemhenzene, penteclilorophenol, phthalid, tolylfluanid, N{4—chioro—Z—nitiophenyD—Nmethyl—4n methylbenzenesulfonamide, guanidine, dithizmon, validamycin, polyoxin B. pyroquilon, ti'ieyelazole, earpropamid, dicyelomet, i‘enoxzmil, and es thereof. in some embodiments, the bed composition may e at least one additional »-—A KJI fungicidal compound selected from azoxystrobin, blfilluflzhl? eoumethoxysti'obin, counioxystrobin, dimoxystrobin, enestrobui‘m, enoxastrobin, fenaminstro‘oin, fenoxystrobm, flufenoxystrobin, fluoxastmbin:jiaxiangiunzhi, kresoxim—methyl, mandestrebin, metominostrobin, oiysastiobin, picoxysti'ohin, pyiaclosti'obini pyiametostrobin, pyi'aoxystrobin, triclopyi'icarb, trilloxystrobin, methyl 2—{2—{25— ”>044‘ dimethylplienyl oxyn'ietliyl)plienyl i—3-methoxydon/late, azaeonazele, bitertanol, biomuconazole, oyproeonazole, difeiioconazole, dinieonazole, diniconazole—M, epoxiconazole, fen‘bueonazole, fliiquinconazole, flusilazole, afol, hexaconazole, imibeneonazele, ipeonazole, meteonazole, myelobutanil, oxpooonazole, paelobutrazolee pencoiidzole onezole? ioconazole nazole tebnceiiazole, tetideonezole, triadimefon. ti‘iadimenol, ti‘iticonazole, azolei imazalil, azoate, procliloraz, triflnmizole, pyrimidines, Fenai'imolj nuarimol, pyrifenox, triforine, and mixtures thereof.

In some embodiments, the described composition may e at least one additional fungicidal compound ed from benodanil, bixafen, id, earboxin, fenfuram, i'am} tlutolanil; fluxapyi'oxad, furametpyi', isopyrazam, mepi‘onil, oxycar‘ooxin, pentlufen, peinliiopymd, sedexane, thilluzamide, and mixtures thereof. in some embodimenta the described. composition may include at least one additional fungicidal compound selected from azoxysti'obin, ximnmetliyl? pieoxystiobin, pyi‘eelostrobin, trifloxystrobin, onazole, lenbueonazole, myclobutenil} pi'opiconazole, ooonamle, tehnoonazolej and mixtures thereof. -72“..4 ' in some embodiments, the escribed fungicidal composition may include the fungicidal compound pyraclostrobin, lo, some ments, the described fungicidal composition may include the ftuigicidal compound protliioconazole.

[A In some embodiments, the described fungicidal composition may include the fungicidal compound propiconazole. in some embodiments, the described fungicidal composition that includes at least one additional fungicidal compound may show synergistic idal activity. in some embodiments the tiingicidal ition described herein may comprise, l. O with. respect to the composition, from about 1 gram active ingredient per liter (g ai/L) to about 200 g ai/L, from about 5 g ai/L to about 175 g ai/L, front about 10 g ai/L to about 150 g ai/L, from about 20 g ai/L to about 150 g ai/L, from about 2.0 g ai/L to about 125 g ai/L, from about 20 g ai/L to about 100 g ai/L, from about 20 g ai/ls to about 90 g ai/L, from about 30 g ai/L to about 90 g ai/L, from about 40 g ai/L- to about 90 g ai/L, from about 40 g ai/L to about »-—A kit 80 g ai/L, from about 45 g ai/L to about '75 g ai/L, or from about 45 g ai/L to about 70 g ai/L of the at least one additional fungicidal compound. The fungicidal composition described herein may also comprise from about from about 30 g rat/1., to about 150 g ai/L, from about 40 g ai/L to about 150 g ai/L, from about 50 g ai/L to about 150 g ai/L, from about 60 g ai/L to about 150 g ai/L, from about 70 g ai/L to about 150 g ai/L, from about 80 g ai/L to about 150 to44‘ g iii/L, from about 90 g ai/L to about 150 g ai/L, from about 100 g ai/I to about 150 g ai/L, from about 110 g ai/l... to about 150 g ai/L, from about 1.20 g ai./l_, to about 150 g ail/1..., from about 125 g ai/L to about 140 g ai/L, or from about 125 g ai/L to about 135 g ai/L of the at least one additional fungicidal compound.

E. Adjuvants Adjuvants are compounds which have negligible or ev en no idal ty lves, and which improve the biological performance of a pesticidal composition on one or more target pests. Examples of such adjuvants may include surfactants such as alcohol ethoxylates, alityi naphthalene sulphonates, alkyl pliosplionates, alitylbenzene sulphonates, benzy1dimetbylcocalkyl ammonium salts, sorbitan ester ethoxylates, and modified silicones; also, mineral or vegetable oils, and other aries. Further examples of adios ants are 1isted by Knowles in, “Adjuvants and Additives,” Agrow Reports D8256, T&F lnfornta UK, 2006, Chapter 51 l'n some ments, the fungicidal composition described herein may include an adj uvant to in'iprove fungici d at performance.

In some embodiments, the fungicidal composition described herein may include an adjutrant to improve fungicidal performance selected from the class of modified [J] organosilicone surfactants such as, for example, the poly ether ed organopolysiloxanes such as Brealothmffs) $233, which is available from Eyonilt Industries (Parsippany, NJ).

In some embodiments, the idal composition described herein may e an adj uyant to improve fungicidal performance selected from the class of all<yl phosphonate ants such as, for example, bis (Z—ethylhexyl) Z—ethylhexylphosphonate (also known as BEEP), which is available from Rhodia (Cranberry, NJ). in some embodiments, nou~ionic surfactants such as, for example, a tridecyl alcohol ethoxylate (ie, Synperonic‘M 13/ i0) may serve as an adj uvant that improves the idal. performance of the fungicidal composition described herein. l'n some ments, the fungicidal composition described herein may include, with respect to the composition, from about l gfL to about 200 g/L of one or more adiuvauts used to improve fungicidal performance. in some embodiments, the fungicidal composition may include from about 1 g/L to about 150 g/L, from about 5 g/L to about 150 g/L, from about it} g/L to about 150 g/,L from about 2U g/L to about l50 g/L, from about 25 g/L to about bill g/L, from about 30 g/L to about l30 g/L, from about 35 g/L to about l25 g/L, from about 40 g/L to about 120 g/L, from about 40 g/L to about i ll) g/l from about 40 g/L to about lull g/L, from about 40 g/L to about 90 g/L, from about 40 g/L to about 80 g/L, from about 40 g/L to about 70 g/L, from about 50 g/L to about 70 g/L, from about 40 g/L to about l30 g/L, from about 50 g/I to about 120 g/l from about 60 g/L to about £20 g/L, from about 70 g/L to about lZO g/L, from about 80 g/L to about no g/L, from about 90 g/L to about 120 g/L, or k) U} from about l00 g/L to about 120 g/L, of one or more adjuvants used to improve idal performance, F. Storage ity As used herein, stable compositions are compositions that are stable physically and/or chemically for defined periods of time to the environments in which they are produced, transported and/or stored. Aspects of stable compositions include, but are not limited to: al stability at teirrperatures that rangt from about 0 CC to about 54 DC, homogeneity, -24.- pourability, liquids that form little or no precipitated solids or crystals or exhibit little or no phase separation, compositions that readily i‘y when poured into a spray tank of water and retain their biological efficacy when applied, for example, by spray application to target pests.

[A In some embodiments, the described composition forms a stable, homogeneous emulsifiable concentrate that does not exhibit appreciable phase separation. under the storage ions. in some embodiments, the described composition exhibits very little change in ity under the e conditions. In some. embodiments, the described composition exhibits very little chemical decomposition of the active ingredient or active ingredients l. 0 under the storage conditions In some embodiments, the described fungicidal composition is stable at temperatures of greater than or equal to about 25 “(I for a period of at least 2, 4, 6 or 8 weeks. In some embodiments, the described composition is stable at temperatures of greater than or equal to about 40 OS for a period of at least 2, 4, 6 or 8 weeks. in some embodiments, the described composition. is stable at temperatures or? greater than or equal to about 54 °C for a period of at least about ‘2 weeks.

In. some embodiments. the described fungicidal composition. does not exhibit or does not significantly exhibit separation, precipitation or crystallization of any of the components at low temperatures. In some embodiments, the described fungicidal composition remains as soa.“ a homogeneous en'iulsii'iable concentrate after storage for at least about 2 weeks at temperatures below about 20 °C, below about 10 0C, or equal to or less than about 5 °C, or equal to or less than about 0 0C, or equal to or less than about _5 0C, or equal to or less than about —lb “(3. in n embodiments, the compositions are stable at these temperatures for at least about 2, All (a, or 8 weelts.

In some embodiments, the bed fungicidal composition remains as a homogeneous concentrate after subjecting it to freeze/thaw (IT/T) conditions for at least about 2. or 4 weeks where the temperature is cycled i about ~l0 0C to about 40 CC every 24 hours.

In some embodiments, the storage stability of the described firngicidal ition may be dependent on one or more ingredients and their tration in the composition.

Such ingredients may include, but are not limited to, the c compounds that comprise the water immiscible organic solvent, the nonionic surfactant, the at least one additional idal compound, dialkylamines such as dimethylarnine that are present in or formed from the NN—dialltylcarboxamides and water in some embodiments, the chemical stability of the active ingredient or active ients in the described fimgicidal composition may be ed by including a hetone [A or an l in the composition. in some embodiments, the chemical. stability of the active ingredient or active ingredients in the described fungicidal composition may be improved by including a nonionic surfactant in the composition. in some embodiments, the chemical stability of the active ingredient or active l. O ingredients in the described fungicidal composition may be improved by eliminating or reducing the amount of a diallrylamine in the composition.

In some embodiments, the al stability of the active ingredient or active ingredients in the described fungicidal composition may be ed by eliminating or reducing the amount of water in the ition. y—i KJI ln some embodiments, the chemical stability of the first active ingredient in the described fungicidal composition may be reduced by adding at least one additional fungicidal compound to the composition.

G. Methods of Preparation and Use Also described herein is a process or method for the preparation of the described idal composition which includes mixing together the one or more fungicide active ingredients, the inert ingredients and the water immiscible organic solvent to form a stable, boniogenous, emulsifiable concentrate that y emulsifies to form a stable, homogeneous, emulsion when added to water. in some embodiments, the fungicidal composition (enrulsitiable concentrate) described herein may be prepared by the steps of: ( l) preparing a solution of the first fungicidal compound. in the water immiscible organic solvent; (2) adding one or more surfactants to the solution prepared in step (I) to form a solution; (3) optionally, adding at least one additional fungicidal compound to the on prepared in step (2); and “'26? (4) ally, adding any additional compatible active or inert ingredients to the solution prepared in step (3) to from a solution.

The described fungicidal composition may also be ed by changing the relative order of the steps, or adding or eliminating steps to the preparation described herein as may [A be y determined by one of ordinary skill in the art.

The disclosure furthermore relates to an emulsion obtainable (preferably obtained) by mixing water with the eniulsitiable concentrate described herein. The emulsion normally arises spontaneously upon mixing. in most cases, the emulsion is an oil—in~water emulsion, The mixing ratio of water to trate may he in the range of from lt‘lllll to 1 up to l to l, l. O preferably 200 to l up to 3 to 1.

Also provided herein is a method of controlling plant derived fungal pathogens or diseases comprising contacting the tion or an area adjacent thereto to t the growth of the fungal pathogens or diseases a fungicidally effective amount of a fungicidal composition comprising: »-—A kit a) a idal compound of the Formula b) at least one ionic surfactant; c) at least one nonionic surfactant; d) an acetate ester; toat e) an “MN—diallrylcarhoxarnide; and f“) optionally, at least one ofa ketone and an alcohol Plant fungal ens that may be controlled by the described fungicidal compositions e ringworm mac-r Pace-limo trz'ttcma, rlzifycosphaereila grammicola, Pacoz‘m’a triticimz, Puccinia striz'formz’s, Venturia inaequalis, Ustz'lago mrigidis, Uncinula -272 necator, Rhynclwspormm secaz’z‘s, Leplosphaeria nou’orum, Adagnaport/te , Mortiimza _,r‘i*ucticoia, Pseudoperonospora cubensz‘sz Pseudocercarporello hemotrt'choldes, Phakopsom parity/Nazi, Phaeosphaeria nor/forum, ria gramirzz‘s ]; ria grammar izordei, Eryszphe Ciclzoraceamm, Ezyszphe g'i‘aamz‘ms, Giomeret’ia iagenarz‘am, (L'ercospora beneath, Alternorz‘a soldier, Rhizoct’omfo salami, Plasn’topom vitlcola, Pitt/tophthom mféstcms, Pyricularia oryzae, and Byrenophom fares.

Plant fungal diseases that may be controlled by the described ftmgicidal compositions include anthracnose, blasts, is, brown rust, r smut, brown rot, downy mildew, fusariuni, powdery mildew, rusts, glurne hlotch, leaf hlotch, net hlotch, sheath , stripe l. O rust, scab, eye spot, leaf spot, early , and late blight. in some embodiments, the described idal ition, after spray application to plant surfaces, exhibits rainfast properties by offering good fungicidal efficacy after re to rain or other moisture causing events This described method includes use of the described fungicidal composition for »-—A kit protecting a plant against attack by a phytopathogenic organism or the ent ofa plant already infested by a phytopatlrogenic organism, comprising the step of applying the described fungicidal ition: to soil, a plant, a part of a plant, foliage, flowers, fruit, and/or seeds, or any surface adjacent to a plant in a disease inhibiting and phytologically acceptable amount. The term “disease inhibiting and phytologically acceptable amount” to44‘ refers to an amount of a nd that kills or inhibits the plant disease for which control is desired, in an amount not significantly toxic to the plant being treated The exact concentration of active compound required varies with the fungal disease to he controlled, the type ot‘formulations employed, the method of application, the particular plant species, climate conditions, and the like, as is well known in the art The fungicidal compositions described herein may optionally be diluted in an aqueous spray mixture for agricultural application such as for the control of phytopathogenic fungi in crop fields. Such compositions are typically diluted with an inert carrier, such as water, before application. The diluted compositions“, which are usually applied, for example, to crops, the locus of crops or the locus of where athogenic fungi may eventually emerge, in some ments include about 0000i to about l weight percent of the active ingredient or from 0.0% to about 1 weight percent of the active ingredient, The present compositions can he applied, for example, to crop plants or their locus by the use of tional ground or aerial Sprayers, and hy other conventional means known to those skilled in the art.

H. l ients The compositions disclosed herein may optionally include inert formulation ingredients such as, but not limited to, dispersants, surfactants and wetting agents These optional ineit ients may include tants conventionally used in the art of VJ] tbrmulation that are described, inter after, in cheon’s Detergents and Einulsiliers Annual,” MC Publishing Corp, Ridgewood, New Jersey, l998 and in the “Encyclopedia of Surfactants,” Vol. l—lll, Chemical Publishing Co, New York, l 'l'hese surface—active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, ding agents, or for other purposes. l0 in addition to the specific methods and itions set forth above, the s and compositions described herein. also may include compositions comprising one or more additional compatible ingredients. These additional ingredients may include, for example, one or more pesticides or other ingredients, which may be dissolved or dispersed in the composition and may e selected. from ides, algicides, antifeedants, avicides, p—d {)1 bactericides, bird repellents, terilants, defoliants, desiccants, disinfectants, fungicides, herbicide safeners, herbicides, insect attractants, insecticides, insect repellents, mammal repellents, mating disrupters, molluscicides, nematicides, plant activators, plant growth regulators, rodenticides, semiochemicals, synergists, and virucides. Also, any other onal ingredients providing functional utility such as, for example, antifoam agents, antimicrobial agents, buffers, corrosion inhibitors, dispersing agents, dyes, ti'agrants, freezing point depressants, neutralizing agents, odorants, penetration aids, sequestering agents, spray drift control agents, spreading agents, stabilizers, sticking agents, viscosity—modifying additives, water soluble solvents and the like, may be included in these compositions.

When the bed compositions are used in combination with the additional active ingredients such as, for example, insecticide active ingredients, the compositions described herein can be formulated with the other active ingredient or active ients as premix concentrates, tankwrniiied in water with the other active ingredient or active ingredients for spray application, or d sequentially with the other active ii'igredient or active ingredients in separate spray applications.

The compositions and methods described herein may he used in controlling fungal diseases in crops possessing single, multiple or stacked genomic traits conferring tolerance to one or more herbicide chemistries and/or tors with single or multiple modes of action -29, 2015/068011 E. Examples The following Examples are presented to illustrate various aspects of the compositions described, herein, and. should not be construed as limitations to the oleirns) Example I : Preparation ofRepresentative Samples off/lie bed U: Fungicidal Composition Table 1. Funnieidal Cmngositions Described Herein legteilient Role Amount (gilt) lst fimgicide cmpd active ingredient l 2nd fungicide enipd. active ingredient “urfactant surfactant eimilsifier surfactant emulsifier organosilioone adjuvant it) — 100 ketone solvent 0 — 500 g acetate ester solvent it) — 750 \Jl‘xdiaiktlearbr\\arnide+SOIVLHLlllbOO nolydinietliylsiloxene antifoani 0.01 - 1 Also known as an N,N-dinietliyl fatty acid amide.

Sainnle l: An emulsion concentrate ing Compound A as the active ingredient was prepared. using the ingredients in Table 2 and as described in the steps below {indicated values are g per 100ml formulation): Table 2. Sam le 1 Fun-jewel Connoeltien i twig-midi: cmpd nd A, 85% tech. ‘- surfactant Nanse EVM 70/213 sj“cone Breakthm $233 500 aceiatfi ester bailzyl acetate 46 81 N,Nwdialkyloatboxamide Hal oomicl M3840l 19-03 polydimethylsiloxene SAG 35172 - (E) An active ingredient premix of cy clohexanone, benzyl acetate, Hallcomid M—fi—lt) and Compound A was prepared. (2) The premix, from (1) was warmed to 35—40‘3C and stirred until a clear solution was obtained. (3) The remaining ingredients were added to the premix [A followed by mixing until a uniform composition was obtained.

Sample 2: An emulsion concentrate sing Compound A and prothioconazole active ingredients was prepared using the ingredients in Table 3 and as described in the steps below ated l. 0 values are g per lilonili formulation): Table 3. Samale 2 Funwieidal (Toingosition 1“ fungicide cmpd Compound A, 859/5 cal protliioconazole 969/5 tech. _ Nansa EVM 70ers I ' organosilicone Breakthru 82.33 5.00 Benzyl acetate 42..“ NN' Hallconiid M~8~ltt 17.11 diallry lcarboxaniide polydimethylsiloxane (E) An active ingredient premix of cy clohexanone, benxyl acetate, Hallcomid M—E—lO, protliioconazole and Compound A was prepared. (2) The premix from (i) was stirred until a clear solution was ed. (3) The remaining ingredients were added to the premix followed by mixing until a m ition was obtained.

An emulsion concentrate comprising Compound A and pyraclostrobin active ients was prepared using the ingredients in Table 4 and as described in the steps below (indicated values are g per lilonili formulation): Table 4. Samele 3 Funwieidal (Toinnosition 2015/068011 1St fungicide cmpd Compound A, 85% technical 2“ fungicide cmpd pyraciestrobin 98% tech. surfactant Nansa EVM 79/215 surfactant surfactant Synpemnic 1 3/10 crganosiiiccne Breakthru 5233 ketcne Cyclohexanone acetate ester Benzyi acetate N’N" i—iancomtd M-8~i 0 diaikyicarhcxamide‘ poly din'ieti'iy lsiiexane SAG 15 72 (i) A solvent premix of cyciohexanone, benzyi acetate and Haiiconiid M—S—EO was prepared. (2) The premix from (I) was stirred until a clear en was obtained. {3) The surfactants, Ui adj uvant and an ti i'cai'nii'ig agent are added to the premix foiiowed by mixing until a m ition was obtained. (4) The pyrachistrebin technical active ingredient was heated until moiten (70°C) and then added to the premix prepared in step (3) whiist mixing. (5) The Compound A technical active ingredient was added to the premix followed by mixing uiitii a uniform composition was obtained Sample 4: An emulsion concentrate comprising nd, A and prethiecenazeie active ingredients was prepared using the ingredients in Tahie 5 and as described in the steps beicw (indicated values are g per iOOmL flirmuiaticn): Tabie 5. Sam ie 4 Functctdafi Cam mitten ltetone Cycloliexanone acetate ester Benzyl acetate NM“ Hallcomid M~S~lO di al kyloarboxamide polydiinethylsiloxane SAG 1572 __________________________________________________________________________________________________________________________________________________________________________ ( l) A solvent premix, of cyclohexanone, benzyl e and Hallconiid M—S—EO was prepared. (2) The premix from (1) was stirred until a clear on was obtained. (3)1‘he surfactants, adj uv ant and antifitarning agent were added to the premix followed by mixing until a Ui uniform composition was obtained. (4) The protl'iioconazole and Compound A tecl'inical active ingredients VVSI‘C added to the premix followed by mixing until a uniform composition was obtained.

Sample 5: An emulsion trate comprising Compound A and pyraclostrobin active ingredients was ed using the ingredients and amounts listed in Table 6 in a manner r to that described for Sample 3 (indicated values are g per 1 L formulation): Table 63., Samgle 5 Fungicidal Comnositien 1‘ fungicide empd Compound A, 85% tech. 2“ timgicide empd pyraclostrobin 98% tech. surfactant Nansa EVM 70/ZE‘. surfactant Toxiinul 8320 organosiligom Breaktbrti 8233 ketone Cycloliexanone e ester Benzyl acetate N,N— Halleomid M-S—lo diallgylcarboxaniide polydirnetbyisiloxane SAG 1572 Saninle 6: An emulsion concentrate comprising Compound A and proihioeonazole active ingredients was prepared using the ingredients and emoui'its listed in Table 7 iii a manner similar to that described fm Sample3(indicated values are iii 91ams per {Mimi formulation): Table ‘7. Sam le 6 idal Com asitien Cmnpoimd A, 84% lSt fungicide cmpd teclim. cal “ fungicide empri protliioeonezoie 96% tech.

—NaiisaEVM 70/21:; — —Synperonic 13/10 — Benzyl acetate EN" Helicomid M—éiuii) . diellaylearboxairii ale.

Sample 7: An emulsion concentrate comprising Compound A and prothioconazoie active ingredients was ed using the ients and amounts listed in Table 8 iii a, manner similar to that described for Sample 3 (indicated values are in grams): Table 8. Samde ‘7 F1111 'icidal Cam esitien Cempound A, 84% ‘ fungicide cmpd technical_ 2" fimgic-ide cmpd prethiocoriazole 96% tech. — Nansa, EVM 70/215 —Toximui 3320 roiiie 13/10 Halloomid M—8 it) - dialiiy lcarboxamide Example 2: Solubilizy off’imgicidal Aciz‘ve Ingrediems in Organic Solvenzs a) Relative solubility of Compound A and oeonazole in c solvents with low solubility in water.

To prepare an effective EC oompositi on comprising Compound A and prothiooonazole [Jr the ing solvent attributes must be ed: 9 Compound A solubility needs to be above 10 wt‘.’/ii a protliioconezole solubility needs to be above 20 Will/é) a water solubility of solvent candidates should be below about fig/L or 0.5% so that good emulsion stability will be achieved when the EC is added to water Infilllllélllfiili 'l‘he approximate solubility of Compound A was determined by mixing a known mass oi‘the active ingredient with an increasing mass of each solvent at ambient temperature. For example, 0.2g ol‘Coinpound A was mixed with l.38g of cycloliexanone giving a clear solution comprising l2.6% w/w Compound A. exanone was therefore classified as a very good solvent for nd A as it offered “High” solubility (see following table) and was included for further evaluation. The solubility of Compound A in the solvents used in this ing procedure was generally classified within the following coneentration ranges: Compound A Relative Solubility Solubilit 'Wt% Very Low Prothioennnzole Rl‘fi‘3 2i “8 Shirl},q) u i ll Sfllubih‘ '° ' “Ito/0, >30 High >20 to ‘30 Medium to 20 Low < 10 Very Low Table 9 shows the relative solubility of Compound A and prothiooonazole in a variety of c solvents. 2015/068011 Tabie 9. Reiative Selubiiitv {11’ (71111190111111 A and Prothiamnamfie E11 ()1: 1111113 8111171111115 111 Ambient Tem 1111111111111 8011763111 S0111b1 11vnof S11111b1111‘1m01 S_0__1v6111111 Com0111111 A 1’1011110wmvole Water 1/L—-_11 Cyclohaxanone Methyl—5{D1 1116:1113’1211111110)—2— Methyl-5~0XO 0 10316 yl 01011311011116 and. lens 13211110111116 13611111111311.1011; acid Z—me‘Ihyl E 511111116111111 1 Bum e 2150131013571 1391120319 N N 1111111311311 fatty 2113111 amides Tributoxy ethyl phosphate — 1311111 Viisc1ble D1at11716115’ e gIlvCO11110110811171§ 7 ,81gb,. M1501ble. , “ Lew ether _ _ d1111611 11I 3 eats SQ1 1' f 1111111 1c. , 7 ’ LQW 1.11.111 53 34111111111: and 51113011111:, 11151113 Polyethylene giycol Miscible Polypropylene glycol —' Miscible — -— I13311111211611 from a survey of the tu1e,2111isc1b1e means totally soiuble111 water U1 111 all amounts; 3Z~ethylhexy1 1111:1318 / Compeund A mimme frames 5110 0C. '36? b) Solubility of nd A and pr‘othioeonazole in benzyl aeetate/AlVlDSll} blends at 10°C.

A study of the Compound A and prothiooonazole solubility in blends of benzyl acetate /' AMDSlO was conducted. To each solvent blend both actives were added until each [A was saturated and the resulting mixtures were then stored at lll°C until equilibrium was ed. Aliquots of the supernatant layer were taken from each , filtered (ll/45nd) mesh) and analyzed by HPLC to determine the solution concentration of each active in the blends. Table 10 shows the results.

Table it). Solubilitv of a Mixture of d A and Prothiocenazole in Benzvl Acetate—AMDSH} Blends at 13°C Proportion ot‘Benzyl Prothioeonazole Solubility.. .. , ,, , x , , acetate to AMD810 in l Compound A Solubility I o o/ u" "3 0 '1 at ll} C (/0 ww)i , ,-at W C (/0 V\7/Vt)' Blend (“$96) ' ' 4.3 c) Solubility of Compound A and prothioeonazole in benzyl acetate AMDSlt‘; cyclohexanone blends at 10°C.

The weight on of each t was tested at a variety ot‘levels (from 0 to l) in the various blends shown in Table ll” A total of 20 g of each solvent blend was prepared per sample. For example, one of the blends (Blend 4) was prepared by combining eyelohexanone 0.2 (4g), benzyl acetate 02 (4g) and AMDSlO {l6 (12g). To Blend 4 were added amounts of Compound A and prothiooonazole technical active ingredients to achieve saturation concentrations of each. The samples were then stored at 10°C for one week and then were analysed for soluble active ingredient content. The results are shown in Table ll, Table 11. lit' of Com onnd A and Prothioeonazole in Benzvl Acetate I’ AMD81G/ C ‘elohexanone Blends at 10°C :2 a fiolvent Ratlolwelgnt fraction} iw Prethloconazole “Jill...El cl l l Number Benzyi Cyclohexanonez acetate AMDSIG fiolubility (‘36 w/w) @ 10"C 4 0.2 02 06 62 32.9 Example 3: Storage Stability esemaZive Samples thhe Descrified idal Composition a) Accelerated e stability study of Compound A in liquid compositions [)1 comprising benzyl acetate), AMD 810 and a third solvent.

The stability of Compound A in a variety of liquid compositions stored at 54 °C for 2 weeks is slimm in Table 1'2. The test positions were prepared in a manner similar to that described in Example 1 using one or more of Compound A, prothiooonazoiel pyraclostrobinl beiizyi acetate, and AMD 810, and a third solvent chosen from cyclohexanone, acetophenone, 241eptanone, 2-heptzmol, oleyl alcohol or 2-ethylliexanol.

Table 12. Stabili of Com mind A in Li “ill Com ns Comrisin Benzvl A cetate AMD 31% and a Third Solvent after Storage for 2; Weeks at 54 “C Comgosltlon gwt‘yo} Cgmmund ’ ' ' ' A after Third Solve-tat 5 Prothio-- Pvraelou = W5 A i Third (’m:;:nd commie sin-chin a I. 501%“; retention; Ell)Elf) ----- -—-4;.\0 Determined by HM(J analy sis; Composition includes an emulsifier blend (14.711194); sing calcium dodecylhenzene sull‘onate, } ethylene oxide/propylene oxide block polymer, and ti‘idec-yl alcohol ethoxylate.

Exam [e 4 Siorage Siabii’ziy aadi’fililzaion ofiSampZe 1 in Waier ()1 21} Storage itv of Sample 1: Sample 1 was stored at 54 °C for 2 weeks in a closed container. The sample remained as a clear, neous yellow liquid with no solids formation or phase sepai.airon dining the storage period HPLC anahsis showed 976% retention of Compound A after the storage period.

Sample 1 was stored at —l() 0C for 1 week in a Closed ner following ClPAC Method 39.3. The sample remained as a clear homogeneous yellow liquid with no crystallization occurring.

Sample 1 was stored in a. closed container at freeze—thaw conditions where the temperature was cycled between —l() 0C and 40 0C every 24 hours for 4 weeks. The sample remained as a homogeneous liquid after storage. b) Dilution ofSample l in rt water: Following {IlPAC Method 36.3, a l l‘l’lL aliquot of Sample l was diluted in 1011 mL of 34-2 ppm hardness water at room temperature to readily form a uniform, Oll'll’l'SV-EICII emulsion that maintained its stability at rt for at least 24 hours. No crystallization of Compound A was evident in the emulsion. e) on of Sarngle l in 5 0C water: Following ClPAC Method 36.3, a l niL aliquot of Sample 1 was diluted in 100 niL of 342 ppm hardness water at 5 °C to readily form a uniform, oil—in—water emulsion that maintained its stability at rt for at least 24 hours. No crystallization of Compound A was evident in the emulsion.

[J] d) Storage stabilitv of Sample 6; Sample 6 was stored at 54 °C for ’2 weeks in a closed container. The sample remained as a clear, homogeneous yellow liquid with no solids formation or phase separation during the e period. HPLC analysis showed 91% retention of Compound A after the storage period. e) Storage stability of Sample '7: Sample 7 was stored at 54 "C for 2 weeks in a closed container. The sample remained as a. clear, neous yellow liquid with no solids formation or phase separation during the storage period. HPl.,C is showed 91% retention of Compound A after the storage period.

Exam' [6 5: Evaluation oft/lie Described Fungicidal Compositions for Disease Confro! a) Comparison of disease control using 3 EC formulations comprising active ingredient Compound A that differ in their water ible organic solvent composition. llvlethods: The fungicide formulations sing Compound A were applied to wheat ngs (2 leaf stage) with the use of a track sprayer (Beirris) in a spray volume equal to 200 Ultra. Five concentrations of active ingredient were used. The concentrations used were 40.3, 13.4, 4.48 and 1.49 g ai/lia. Plants were inoculated in 3 day curative (313C) and one day protectant (EDP) tests. Plants were challenged with both PUCCRT (Puccinia ina; wheat brown rust) and SEP'l'TR (S eptoria tritici; wheat leaf hlotoh) fungal N (.1; pathogens. A total of 3 ations were used for each timing and pathogen combination.

Disease caused by PUCCRT was evaluated ’7 days after inoculation and disease caused by SEPT'l‘R was evaluated 18—21 days after inoculation. The % tissue infected was determined and then the % disease control was calculated using the following on: % disease control (l —ohserved disease/disease from the untreated)* 100.

Materials: The einulsilialile concentrate (EC) formulations shown in Table 13 were used in ide spray ations for the control of i a tritici (wheat leaf blotch) and Puccini a. triticina (wheat brown rust) on, wheat plants, The Sample A, and, Sample B comparative formulations comprised of cyclohexanone/Aromatic 100 and N [‘1‘ methylpyrroiidone ,I’Arornatic ZOOND, tively, as the water immiscible organic solvents, whereas the Sample C formulation comprised. of benzyl e/ N,N—dimetl1yl fatty acid amide as the water inmiiscible organic solvent.

Table 13. Composition oflflC Foimttlatlons Used in Funleide swan A- llcatiens 'l'ensiofix N98l ii—irr Sample A. .

EC Tensiofix N9839HF —Sotvem _XctiveInYredient Aromatic ZOllND Salt/em: Active Ingredient 50 /l alcohol, ethOX/lated N,N~dimethrl fatt acid amide Disease control data: Table 14 shows the average disease control of fungicide spray applications for the control of Septoria i (SEPTTR; wheat leaf blotch) and Puccinia triticina (PUCCRT; \t’lieat brown rust) on Wll eat plants.

Table 14. Disease Control on Wheat Plants with Various S m A lied Formulations Com risin Com ouml A pathogen Compound A Application Rate (g ai/ha) l-oirnu ation Appicd. and g . _ l l’ Application 147, 4.48 13.4 40.3 Tim mg ' Average % Disease Control -4. j - none _ inocuiated Pnccn‘r 10:9 none — dean PUCCRT 113.9 100 Sam. 1e A - com arati've 27 97’ 99 Semiie B — com ai'etive Samie C none - inoculated v. z a t) 0 (1 5 none , eiean . :r":'.- Sam 1e A — com ntaiive SEPTTR IDP Sam 16: B - com Jamtive SEPTTR 1UP ' SEP'HTTR mp ' none - eieen SEP'F'TR 30C SEP'F'TR 3121C SEPT??? 313C SEPTTR 3DC Samfle C + 1wcol 59-41 SEPTTR 313C . “‘1rycoi 5941 (BASE; tridecyi alcohol(E.0191IS an adiuvant added tothe respective spray ons at a concentration of 0.115 wt/"’oto boost fungicide efficacy. b) Disease contro1 using described itions sing Compound A andj optionaiiy, either prothieonazoie or pyiaclostro‘oin, before and; after a simulated rain event to KJ! evaluate minfastness ofthe applied compositions.

Methods: “Yuma” wheat was used as the host piant in these fungicide efficacy ti‘ialsi Seed1ings were sprayed when the seeond leaf was 11,1113' expanded (8 days after g). The fungus Pucc'inz‘a triticz’na (PUCCRT; wheat brown rust) was used as the test organism in the efficacy bioassay. The amount of rain applied after fungicide applications was 10 mm. Four 2015/068011 separate rain treatments were used with each fungicide treatment. The rain treatments w ere no rain, and rain at l, 30, or 60 minutes after fimgicide application. There were three replicate for each combination of fungicide, rate and ll interval. All, fungicide formulations were diluted in water to achieve the desired spray concentrations. ides (“h were applied with a track spray er set at 150 liters per hectare delivery volume at 2.1 atrn and a speed of 1.9 km/h. A. flat fan. 'l‘eeJet 8003 nozzle tip was used The nozzle tip Viras 50 em. above the top of the seedlings. All ide formulations were applied at 1/4, 1/8 and 1/16 of the recommended field rate (1X). Table 15 shows the results from these trials. l, 0 Table 15. Bisease Control on Wheat Piants with Various Sanity Anglied Formulations Corngrising nd A after Simulated Rain Events Active % Bisease Control of PUCCRT it)? ingredient (1x Formulation Weather event at indicated Rate of Applieatienl Rate) no rain Compound A I rain at 30 (130 g ai/ha) minutes rain at 60 minutes Compound A + oconazoie rain at 30 (100 + 200 minutes get/ha) rain at 60 no rain Compound A + rain at 1 minute prothioconazole rain at 30 Sample 4 (100 + 200 minutes g ai/ha) rain at 60 minutes Compound A + pyraclostrobin rain at 1 minute (100 «2- 125 rain at 30 g ai/ne) minutes rain at 60 minutes 100 {.9 LC 89 1‘The application rate for each active ingredients arei . t . . . ‘ l/L’l, 1/85 and 1/16, respectively,, I of the 1X rate shown in column .1 for the respective active ingredient.

The present ion is not limited in scope by the embodiments disclosed herein {J} which are intended as illustrations of a few aspects of the invention and any embodiments which are tithetionally equivalent are within the scope of this invention. Various modifications of the processes“, methods? and itions in addition to those shown and bed herein will become apparent to those skilled in the art and are intended to fall within the scope of the appended claims. Further, while only certain representative combinations of the process and method steps and composition components disclosed herein are specifically discussed in the embodiments above? other combinations of the composition components and process and method steps will become apparent to those skilled in the art and also are ed to fall within the scope ot‘the ed . Thus a combination of components or steps may be explicitly mentioned ; however, other combinations of H VJ) components and steps are included, even though not explicitly stated. The term comprising and variations thereof as used herein is used synonymonsly with the term including and variations thereof and are open? non-limi ting terms. -44.“ 1002206687

Claims (35)

1. A fungicidal composition comprising: a) a fungicidal compound of the Formula 5 ; b) at least one ionic surfactant; c) at least one ic surfactant; d) from about 50 g/L to about 700 g/L of benzyl acetate; and e) at least one N,N-dialkylcarboxamide; 10 n the benzyl acetate and the at least one N,N-dialkylcarboxamide together form a water immiscible organic solvent.

2. The fungicidal composition of claim 1, wherein the composition includes: a) from about 1 gram per liter (g/L) to about 200 g/L of the fungicidal compound of the Formula 15 ; 1002206687 b) from about 1 g/L to about 100 g/L of the at least one ionic surfactant, wherein the at least one ionic surfactant includes at least one anionic surfactant; c) from about 1 g/L to about 200 g/L of the at least one nonionic surfactant; d) from about 50 g/L to about 700 g/L of the benzyl e; and 5 e) from about 25 g/L to about 300 g/L of the at least one N,N-dialkylcarboxamide, wherein the at least one N,N-dialkylcarboxamide includes an N,N-dimethyl fatty acid amide.

3. The fungicidal compositions of claim 1, wherein the composition includes from about 1 gram per liter (g/L) to about 200 g/L of the fungicidal nd of the Formula 10 .

4. The fungicidal compositions of any one of claims 1 or 3, wherein the composition includes from about 1 g/L to about 100 g/L of the at least one ionic surfactant, wherein the at least one ionic surfactant es at least one anionic surfactant.

5. The fungicidal compositions of any one of claims 1, 3 or 4, wherein the ition 15 includes from about 1 g/L to about 200 g/L of the at least one nonionic surfactant.

6. The fungicidal compositions of any one of claims 1, 3, 4 or 5, wherein the composition includes from about 25 g/L to about 300 g/L of the at least one N,N-dialkylcarboxamide, wherein the at least one N,N-dialkylcarboxamide includes at least one of an N,N-dimethyl fatty acid amide. 20

7. The idal compositions of any one of claims 1-6, wherein the weight ratio of benzyl acetate : the at least one N,N-dialkylcarboxamide ranges from about 1-10 : 1-10. 6687

8. The fungicidal compositions of any one of claims 1-7, wherein the weight ratio of benzyl acetate : the at least one N,N-dialkylcarboxamide ranges from about 1-5 : 1-2.

9. The fungicidal compositions of any one o claims 1-8, wherein the at least one N,N- dialkylcarboxamide is selected from a group consisting of N,N-dimethylhexanamide, N,N- 5 dimethyloctanamide, N,N-dimethyldecanamide and N,N-dimethyldodecanamide.

10. The fungicidal compositions of any one of claims 1-9, further including at least one additional fungicidal compound.

11. The fungicidal compositions of claim 10, wherein the at least one additional fungicidal compound is ed from a group consisting of azoxystrobin, bifujunzhi, hoxystrobin, 10 coumoxystrobin, dimoxystrobin, enestroburin, enoxastrobin, fenaminstrobin, fenoxystrobin, flufenoxystrobin, fluoxastrobin, jiaxiangjunzhi, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, triclopyricarb, trifloxystrobin, methyl 2-[2-(2,5-dimethylphenyloxymethyl)phenyl] methoxyacrylate, azaconazole, anol, bromuconazole, cyproconazole, difenoconazole, 15 diniconazole, diniconazole-M, epoxiconazole, onazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, il, pefurazoate, prochloraz, mizole, pyrimidines, fenarimol, nuarimol, pyrifenox, and triforine. 20

12. The fungicidal compositions of any one of claims 10-11, wherein the at least one additional fungicidal nd is selected from a group consisting of azoxystrobin, kresoximmethyl , picoxystrobin, ostrobin, trifloxystrobin, epoxiconazole, fenbuconazole, utanil, propiconazole, prothioconazole, and tebuconazole.

13. The fungicidal compositions of any one of claims 10-12, n the at least one 25 additional fungicidal compound is ed from a group consisting of pyraclostrobin, prothioconazole and propiconazole. 1002206687

14. The fungicidal compositions of any one of claims 1-13, further including an adjuvant that improves the fungicidal mance of the composition selected from a group consisting of a non-ionic tant, a polyether modified organopolysiloxane and an alkyl phosphonate.

15. A method of controlling fungal plant pathogens or diseases comprising the steps of 5 contacting the tion or an area adjacent thereto to prevent the growth of the fungal pathogens or diseases with a fungicidally effective amount of a fungicidal composition comprising: a) a fungicidal compound of the Formula 10 b) at least one ionic surfactant; c) at least one nonionic surfactant; d) from about 50 g/L to about 700 g/L of benzyl acetate; and e) at least one N,N-dialkylcarboxamide; wherein the benzyl acetate and the at least one N,N-dialkylcarboxamide together form 15 a water immiscible organic solvent.

16. The method of claim 15, wherein the fungicidal composition includes from about 1 gram per liter (g/L) to about 200 g/L of the idal compound of the Formula 1002206687

17. The methods of any one of claims 15-16, n the fungicidal ition es from about 1 g/L to about 100 g/L of an anionic surfactant of the at least one ionic surfactant, n the at least one ionic surfactant includes at least one anionic surfactant. 5

18. The methods of any one of claims 15-17, wherein the fungicidal composition includes from about 1 g/L to about 200 g/L of the at least one nonionic surfactant.

19. The methods of any one of claims 15-18, wherein the fungicidal composition includes from about 25 g/L to about 300 g/L of the at least one N,N-dialkylcarboxamide , n the at least one N,N-dialkylcarboxamide includes an N,N-dimethyl fatty acid amide. 10

20. The methods of any one of claims 15-19 wherein the weight ratio of benzyl acetate : the at least one N,N-dialkylcarboxamide ranges from about 1-10 : 1-10.

21. The methods of any one of claims 15-20, wherein the weight ratio of benzyl acetate : the N,N-dialkylcarboxamide ranges from about 1-5 : 1-2.

22. The methods of any one of claims 15-21, wherein the at least one N,N- 15 dialkylcarboxamide is selected from a group consisting of N,N-dimethylhexanamide, N,N- dimethyloctanamide, N,N-dimethyldecanamide and N,N-dimethyldodecanamide.

23. The methods of any one of claims 20-22, wherein the water immiscible organic solvent includes benzyl acetate and one or more than one of a fatty acid N,N-dialkylcarboxamide.

24. The methods of any one of claims 15-23, the fungicidal composition further comprising 20 at least one additional fungicidal compound. 1002206687

25. The methods of claim 24, wherein the at least one additional idal compound is ed from a group consisting of azoxystrobin, bifujunzhi, coumethoxystrobin, ystrobin, dimoxystrobin, oburin, enoxastrobin, fenaminstrobin, fenoxystrobin, flufenoxystrobin, fluoxastrobin, jiaxiangjunzhi, kresoxim-methyl, trobin, 5 metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, triclopyricarb, trifloxystrobin, methyl 2-[2-(2,5-dimethylphenyloxymethyl)phenyl] methoxyacrylate, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, afol, hexaconazole, imibenconazole, ipconazole, metconazole, utanil, 10 oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, azole, imazalil, pefurazoate, oraz, triflumizole, pyrimidines, fenarimol, nuarimol, pyrifenox, and triforine.

26. The methods of any one of claims 24-25, wherein the at least one onal fungicidal compound is selected from a group consisting of azoxystrobin, kresoxim-methyl, picoxystrobin, 15 pyraclostrobin, trifloxystrobin, epoxiconazole, fenbuconazole, myclobutanil, propiconazole, prothioconazole, and tebuconazole.

27. The methods of any one of claims 24-26, wherein the at least one additional fungicidal compound is selected from a group consisting of pyraclostrobin, prothioconazole and propiconazole. 20

28. The methods of any one of claims 15-27, the fungicidal composition further comprising an nt that improves the fungicidal performance of the fungicidal composition selected from a group consisting of a non-ionic surfactant, a her modified organopolysiloxane and an alkyl phosphonate.

29. The methods of any one of claims 15-28, wherein the fungal plant pathogens include 25 ia tritici, Puccinia triticina, Mycosphaerella graminicola, ia triticina, Puccinia striiformis, Venturia inaequalis, Ustilago maydis, Uncinula necator, Rhynchosporium secalis, Leptosphaeria nodorum, Magnaporthe grisea, Monilinia fructicola, Pseudoperonospora cubensis, cercosporella herpotrichoides, Phakopsora pachyrhizi, Phaeosphaeria nodorum, ia graminis tritici, Blumeria graminis hordei, Erysiphe cichoracearum, 1002206687 Ezysiphe graaminis, Glomerella lagenarium, pora beticola, Alternaria solani, tonia solani, Plasmopara viticola, Phytophthora infestans, Pyricularia oryzae, and Pyrenophora teres.

30. The methods of any one of claims 15-29, wherein the fungal plant diseases include 5 anthracnose, blasts, botrytis, brown rust, blister smut, brown rot, downy mildew, fusarium, powdery , rusts, glume blotch, leaf blotch, net blotch, sheath blight, stripe rust, scab, eye spot, leaf spot, early blight, and late blight.

31. The compositions or methods of any one of claims 1-30, wherein the at least one ionic surfactant is an anionic surfactant selected from a group consisting of an alkali, alkaline earth 10 and ammonium salt of an alkylarylsulfonic acid.

32. The compositions or s of any one of claims 1-31, wherein the at least one nonionic surfactant is selected from a group consisting of an alcohol initiated EO/PO block copolymer and an alcohol ethoxylate.

33. A fungicidal composition according to claim 1, sing: 15 a) a fungicidal compound of the Formula b) a m salt of an alkylaryl sulfonate; c) an alcohol initiated EO/PO block copolymer; d) a tridecyl l ethoxylate; 20 e) a polyether modified polysiloxane; f) from about 50 g/L to about 700 g/L of benzyl acetate; and 1002206687 g) an N,N-dimethyl fatty acid amide; wherein the benzyl acetate and the at least one N,N-dialkylcarboxamide together form a water immiscible organic solvent.

34. A fungicidal composition according to claim 33, further comprising prothioconazole. 5

35. A fungicidal composition ing to claim 33, further sing pyraclostrobin.