WO2021099350A1

WO2021099350A1 - Composition comprising azole fungicides and fatty acid amides

Info

Publication number: WO2021099350A1
Application number: PCT/EP2020/082476
Authority: WO
Inventors: Paul O'byrne; Robert Williams; Eugene MAHON
Original assignee: Life Scientific Ltd
Priority date: 2019-11-18
Filing date: 2020-11-18
Publication date: 2021-05-27

Abstract

The invention relates to a plant protection composition comprising at least one azole fungicide, and at least one fatty acid amide of formula R1-CO-NR2R3, wherein R1 is a fatty acid derived from a vegetable oil, and R2 and R3 are independently a methyl or an ethyl.

Description

COMPOSITION COMPRISING AZOLE FUNGICIDES AND FATTY ACID AMIDES

FIELD OF DISCLOSURE

[0001] The present technology generally relates to a plant protection composition comprising at least one azole fungicide, and at least one fatty acid amide, more specifically the fatty acid of the fatty acid amide being derived from a vegetable oil.

BACKGROUND OF DISCLOSURE

[0002] The globalization of agriculture has led to crop plants being grown in areas where they may be exposed to new pathogens or new strains of existing fungi to which they may be susceptible. It is estimated that 70% of all major crop diseases are caused by phytopathogenic fungi and thus threaten food supplies worldwide.

[0003] The development of commercial antifungal agents in agriculture began with copper- based Bordeaux mixture in the 19th century. In the 20th century, many new classes of synthetic organic fungicides, including azole fungicides, and compositions thereof werediscovered and have been since described in the literature. However, the biological properties of these compositions are not entirely satisfactory in the areas of pathogenic control, phytotoxicity, and environmental and worker exposure, for example. In particular, the development of fungal resistance to many of these agents, and low biological activity and availability has been an increasing problem with existing compositions. Consequently, there is a growing need for plant protection compositions which have a high biological activity, as well as high plant penetration abilities, and can therefore effectively act on the plant to kill the fungi when infected as such. [0004] Therefore, there is a need for fungicidal compositions which at least overcome some of the above-described problems.

SUMMARY OF DISCLOSURE

[0005] An object of the present technology is to provide an improved fungicidal composition with increased penetration abilities, and therefore improved efficiency in killing fungi infecting plants.

[0006] In various aspects, the present technology relates to a fungicidal composition. The fungicidal composition comprises at least one azole fungicide, and at least one fatty acid amide of formula R1-CO-NR2R3, wherein R1 is a fatty acid derived from a vegetable oil, and R2 and R3 are independently a methyl or an ethyl.

[0007] From another aspect, the present technology relates to an emulsion obtained by mixing said fungicidal composition with a diluent. DD008] From yet another aspect, the present technology relates to a method for improving the penetration of at least one azole fungicide into a plant. The method comprises applying any one or more of said composition and said emulsion, to a plant.

[0009] From a further aspect, the present technology relates to the use of any one or more of said composition, and said emulsion in the protection or treatment of a plant in need thereof. [0010] From a yet further aspect, the present technology relates to a method for controlling one or more harmful fungus comprising contacting the harmful fungus, a habitat thereof, a host thereof, optionally plants, and/or seed, and/or soil, an area and an environment in which plants grow or could grow, and/or materials, plants, seeds, soil, surfaces, and/or spaces which are to be protected from attack or infestation by one or more fungus that are harmful to plants, with an effective amount of any one or more of said composition or said emulsion.

[0011] Embodiments of the presently described fungicidal composition facilitate the penetration of azole fungicides into plants and thereby improve their efficiency.

[0012] Other aspects and features of the present disclosure will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0013] FIG. 1 illustrates a comparison of % radiolabelled prothioconazole cuticle penetration in a composition comprising tall oil fatty acid dimethylamide (E593B) and N,N- dimethyldecanamide (E597A).

[0014] FIG. 2 illustrates a comparison of % radiolabelled prothioconazole cuticle penetration of a prothioconazole: tebuconazole composition comprising tall oil fatty acid dimethylamide (E597C) and N,N-dimethyldecanamide (E597B).

[0015] FIG. 3 illustrates a comparison of the % desthio-prothioconazole content relative to t=0 in plant in a composition comprising tall oil fatty acid dimethylamide (E600D) and N,N- dimethyldecanamide (E600C).

[0016] FIG. 4 illustrates a comparison of the % radiolabelled prothioconazole in plant in a composition comprising tall oil fatty acid dimethylamide (E600D) and N,N-dimethyldecanamide (E600C).

DETAILED DESCRIPTION

[0017] The present disclosure is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the drawings. The disclosure is capable of other embodiments and of being practiced or of being carried out in various ways. Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of "including", "comprising", or "having", "containing", "involving" and variations thereof herein, is meant to encompass the items listed thereafter as well as, optionally, additional items. In the following description, the same numerical references refer to similar elements.

[0018] It must be noted that, as used in this specification and the appended claims, the singular form “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. [0019] As used herein, the term “about” in the context of a given value or range refers to a value or range that is within 20%, preferably within 10%, and more preferably within 5% of the given value or range.

[0020] As used herein, the term “and/or” is to be taken as specific disclosure of each of the two specified features or components with or without the other. For example, “A and/or B” is to be taken as specific disclosure of each of (i) A, (ii) B and (iii) A and B, just as if each is set out individually herein.

[0021] The recitation herein of numerical ranges by endpoints is intended to include all numbers subsumed within that range (e.g., a recitation of 1 to 5 includes 1, 1.25, 1.33, 1.5, 2, 2.75, 3, 3.80, 4, 4.32, and 5).

[0022] As used herein, the terms “formulation” and “composition” as used interchangeably herein are equivalent terms referring to a composition of matter.

[0023] As used herein, the term “plant-protection composition” refers to a composition to be applied on plants protecting them against the harmful effect of a stress.

[0024] As used herein, the term “fungicide” refers to a substance that destroys or controls growth of fungus.

[0025] As used herein, the term “azole” refers to a class of five-membered heterocyclic compounds containing a nitrogen atom and at least one other non-carbon atom (i.e. nitrogen, sulfur, or oxygen) as part of the ring.

[0026] As used herein, the term “fatty acid” refers to a carboxylic acid with a long aliphatic chain, having more than 4 Carbon atoms in the aliphatic chain, which is either saturated or unsaturated. Fatty acids having more than 4 Carbon atoms in the aliphatic chain include fatty acids having more than 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 Carbon atoms, or at least 18 Carbon atoms.

[0027] As used herein, the term “emulsion” refers to a mixture of two or more liquids that are normally immiscible.

[0028] As used herein, the term “protection” refers to protecting plants from harmful organisms, including harmful fungi. [0029] As used herein, the term “treatment” refers to controlling the growth and spread of diseases caused by harmful organisms in a plant, including phytopathogenic fungi.

[0030] Broadly, the present technology is related to a composition comprising at least one azole fungicide, and at least one fatty acid amide. Previously, alkyl carboxylic acid dimethylamides, and more specifically C5-C19 fatty acid amides, have been used to inhibit the crystallization of azole fungicides (US Patent No. 5,206,225, Horstmann et al., incorporated herein by reference), which otherwise block the filters and nozzles of spray equipment used for the application of plant treatment agents. Rochling et al. (US Patent No. 8,124,564, incorporated herein by reference) have also used N,N-dimethyl-n-hexanamide, N,N-dimethyl-n-octanamide, N,N-dimethyl-n-decanamide and N,N-dimethyl-n-dodecanamide, in particular N,N-dimethyl-n- octanamide and N,N-dimethyl-n-decanamide to increase the penetration of agrochemical active substances, including azole fungicides, across the cuticle of a plant to increase the biological activity of plant protection compositions. Other compositions comprising azole fungicides and fatty acid amides have also been described in WO 94/13140, US 2008/262061, EP 3 178 320, US Patent No. 4,713,184, WO 99/02037, WO 93/01801, and US Patent No. 3, 199, 989 (all incorporated herein by reference). Surprisingly, the inventors of the present technology have discovered that N,N-dimethylamides of fatty acids derived from vegetable oils are advantageous over those described in the documents cited above and increase the foliar penetration of azole fungicides, and therefore, by inference, the biological activity of these plant protection compositions. More specifically, the inventors have discovered that tall oil fatty acid dimethylamides improve the effectiveness of azole fungicides.

[0031] Non-limiting examples of azole fungicides suitable for use in the composition of the present technology, include 5-chloro-3-methyl-4-nitro-1H-pyrazole (CMNP); azaconazole; bromuconazole; chlorfenazole; cyproconazole; difenoconazole; diniconazole; dinicon-azole-M; epoxiconazole; enilconazole; etaconazole; etridiazole; fenbuconazole; fluquinconazole; flusilazole; fuberidazole; hexaconazole; imibenconazole; ipfentrifluconazole; ipconazole; mefentrifluconazole; metconazole; oxpoconazole; penconazole; probenazole; propiconazole; prothioconazole; quinconazole; simeconazole; tebuconazole; tetraconazole; thiabendazole; triadimefon; triadimenol; tricyclazole; triticonazole; uniconazole; thiazolecarboxamide; methyl 1 -(2, 3 -dihydro-2,2 -dimethy 1-1 H-inden-1-y 1)-1H-imidazole5-carboxylate; N-3'4'-dichloro-5 fluorobipheny 1-2-y 1)-3-(difluoromethyl)-1 -methyl- 1 H-pyrazole-4 -carboxamide; tebuconazole, triadimenol, triadimefon, epoxiconazole, metconazole, fluquinconazole, cyproconazole, penconazole and prothioconazole, preferably prothioconazole. [0032] In some embodiments, the composition of the present technology may comprise a combination of azole fungicides. In further embodiments, the composition of the present technology may comprise a first azole fungicide and a second azole fungicide. In a preferred embodiment the first azole fungicide is prothioconazole with a second azole fungicide, particularly as listed above. In an even preferred embodiment, the first azole fungicide is prothioconazole and the second azole fungicide is tebuconazole or metconazole.

[0033] In further embodiments, the proportion of the first azole fungicide to the second azole fungicide as defined above may be between about 10: 1 to about 1:10, between about 5 : 1 to about 1:5, between about 2:1 to about 1:3, between about 1:1 to about 1:2, or between about 1:6 to about 1:8, between about 2:1 to about 1:9, between about 2:1 to about 1:8, between about 2:1 to about 1:7, between about 2:1 to about 1:6, between about 2:1 to about 1:5, between about 2:1 to about 1:4, between about 2:1 to about 1:3, between about 2:1 to about 1:2,. In a yet further embodiment, the proportion of the first azole fungicide to the second azole fungicide is 1:1.

[0034] As a preferred embodiment when the first azole fungicide is prothioconazole, the proportion of the first azole fungicide to the second azole fungicide as defined above is between 3:1 to 1:2.

[0035] In a further embodiment the composition may contain with the azole fungicides, alone or a mixture of azole fungicides as defined above, one or more non-azole fungicidal active ingredients. Such non-azole fungicides are known in the art, eventually for their use in combination with one or more azole fungicides. Non-limiting examples of other fungicides include 2-phenylphenol; 8-hydroxyquinoline sulphate; acibenzolar-S-methyl; aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim; anilazine; azoxystrobin; benalaxyl; benalaxyl-M; benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; benzovindiflupyr; bilanafos; bina-pacryl; biphenyl; bitertanol; bixafen; blasticidin-S; boscalid; bupirimate; buthiobate; butylamine; calcium polysulphide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvone; quinomethionate; chlobenthiazone; hloroneb; chlorothalonil; chlozolinate; clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos; ethaboxam; ethirimol; famoxadone; fenamidone; fenapanil; fenarimol; fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; fluindapyr; flumetover; flumorph; fluopyram; fluoromide; fluoxastrobin; flurprimidol; flusulfamide; flutolanil; flutriafol; fluxapyroxad; folpet; fosetyl-Al; fosetyl-sodium; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine; hexachlorobenzene; imazalil; iminoctadine triacetate; iminoctadine tris (albesilate); inpyrfluxam, iodocarb; iprobenfos; iprodione; iprovalicarb; irumamycin; isofetamid; isoflucypram; isoprothiolane; isopyrazam; isovaledione; kasugamycin; kresoxim-m ethyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; methasulfocarb; methfuroxam; metiram; metominostrobin; metsulfovax; mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen; nitrothalisopropyl; noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxycarboxin; oxyfenthiin; pydiflumetofen; pefurazoate; penflufen; pencycuron; penthiopyrad; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; prochloraz; procymidone; propamocarb; propano sine-sodium; propineb; proquinazid; pyraclostrobin; pyrazophos; pyraziflumid; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrine; quinoxyfen; quintozene; sedaxane; silthiofam; spiroxamine; sulfur; tecloftalam; tecnazene; tetcyclacis; thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide; tridemorph; trifloxystrobin; triflumizole; triforine; validamycin A; vinclozolin; zineb; ziram; zoxamide; (28) — N-[24443 -(4-chloropheny 1 )-2-propynyl]oxy]-3-methoxy-phenyl]ethyl]-3-methyl2- [(methylsulfonyeamino]butanamide; 1 -(1 -naphthalenyl)-1H-pyrrole-2,5-dione; 2, 3,5,6- tetrachloro-4-(methylsulfonyl)pyridine; 2-chloro-N-(2,3-dihydro-1,1,3-trimethy 1-1H-inden-4- yl)-3-pyridinecarboxamide; 3,4,5-trichloro-2,6 pyridinedicarbonitrile; actinovate; monopotassium carbonate; N-6-m ethoxy-3 -pyridinyl)cyclopropanecarboxamide; N-buty 1-8- (1,1 -dimethylethyl)-1-oxa-spiro[4,5]decan-3-amine; sodium tetraborate; and copper salts and preparations, such as Bordeaux mixture; copper hydroxide, copper naphthenate; copper oxychloride; copper sulphate; cufraneb; cuprous oxide; mancopper; oxine copper and combinations thereof. Preferred non-azole fungicides used in combination with the azole fungicides are particularly selected among isopyrazam, spiroxamine, bifaxen, fluopyram, benzovindiflypyr, fluoxastrobin, trifloxystrobin and mixtures thereof.

[0036] In further embodiments, the proportion of the total amount of azoles fungicides, alone or in mixtures as defined above, to the non-azole fungicide as defined above may be between about 1:4 and about 2:1, between about 1:3 and about 1:1, between about 1:3 and about 1:2, between about 1:2.5 and about 1:2, between about 1:4 and about 1:3, between about 1:1 and about 4:1, between about 1:1 and about 3:1, between about 1:1 and about 2:1, between about 2:1 to about 3 : 1, or between about 3 : 1 and 4:1. [0037] The fatty acid amide used in the composition of the present technology is of formula R1-CO-NR2R3, wherein R1 is a fatty acid derived from a vegetable oil, and R2 and R3 are independently a methyl or an ethyl. In some embodiments, R1 may be an unbranched or branched, saturated or unsaturated fatty acid. In other embodiments, R1 may be an unbranched and unsaturated alkyl group having 14 to 22 carbon atoms. In further embodiments, R1 may be an unbranched and unsaturated alkyl group having 18 carbon atoms.

[0038] The fatty acid in the fatty acid amide is derived from a vegetable oil. By “fatty acid amide derived from vegetable oils” it is meant that the components of the fatty acids of the natural vegetable oil have been modified to have the structure of R1-CO-NR2R3 as described above. Preferably, at least 50 percent of the fatty acids present in the vegetable oil may be modified to have the structure of R1-CO-NR2R3. More preferably, at least 95 percent of the fatty acids present in the vegetable oil are modified as such. Non-limiting examples of vegetable oils suitable for use in the composition of the present technology include coconut oil, com oil, cottonseed oil, palm oil, soybean oil, peanut oil, canola oil, safflower oil, sunflower oil, babassu oil, castor oil, linseed oil, olive oil, tung oil and tall oil. In some embodiments, the fatty acid is derived from vegetable oils selected from the group consisting of coconut oil, com oil, cottonseed oil, palm oil, soybean oil, and tall oil. In a preferred embodiment, the vegetable oil is tall oil. As seen in Table 1, these oils consist primarily of C16-C18 unsaturated fatty acids (>88%) (Composition and Constants of Fats and Oils, Armour Chemical Division, Chicago, Illinois).

Table 1

[0039] In addition to Palmitic, Oleic and Linoleic acid, tall oil may also comprise a percentage of other acids and saponifiable matter (Heterogeneous Acid-Catalyzed Biodiesel Production from Crude Tall Oil: A Low-Grade and Less Expensive Feedstock. Journal of Wood Chemistry and Technology 35(5), 374-385) (Table 2). Table 2

[0040] In some embodiments, the fatty acid derived from any one or more of the vegetable oils listed above may comprise at least one of Laurie, Myristic, Palmitic, Stearic, Lauroleic, Myristoleic, palmitoleic, Oleic, and Linoleic acid.

[0041] N,N-dimethylamide tall oil fatty acids are commercially available and sold as DMATO on the market. N,N-dimethylamide tall oil fatty acids are also available in compositions wherein the N,N-dimethylamide tall oil fatty acids are diluted with alcohol ethoxylate, and sold as DMAD. In DMAD, the alcohol ethoxylate used to dilute the N,N- dimethylamide tall oil fatty acids consist of, C9-11-iso-C10-rich, ethoxylated in DMAD. In such compositions, the proportion of tall oil to alcohol ethoxylate may be between about 50:50 and about 90:10 , between about 50:50 and about 80:20, between about 50:50 and about 70:30, between about 50:50 and about 60:40, between about 60:40 and about 90:10, between about 60:40 and about 80:20, between about 60:40 and about 70:30, between about 70:30 and about

90:10, between about 70:30 and about 80:20, and between about 80:20 and about 90:10. [0042] In some embodiment the proportion of the at least one azole fungicide to the fatty acid amide of formula R1-CO-NR2R3 defined above is between about 1:1 to about 1:15, between about 1 :2 to about 1 :4, between about 1 :4 to about 1 :6, between about 1 :6 to about 1:8, between about 1:8 to about 1:15, between about 1:1 to about 1:2.5, preferably between about 1:1.5 to about 1:2, and more preferably about 1:2. The amount of azole fungicide in these proportions are based on the total amount of azole fungicides, alone or in mixtures as defined above.

[0043] In one embodiment of the invention, the composition is a premix composition comprising at least one azole fungicide, alone or as a mixture of azole fungicides and possibly with an additional non-azole fungicide, and the fatty acid amide of formula R1-CO-NR2R3 as defined above.

[0044] According to the invention, the proportion of the at least one azole fungicide in the composition of the present technology is between about 4 %w/w to about 60 %w/w of the total composition, including from 10 %w/w to 50 %w/w, particularly from 15 %w/w to 40 %w/w, more particularly from 20 %w/w to 30 %w/w, even more particularly about 25% w/w. The amount of azole fungicides in these proportions are based on the total amount of azole fungicide, alone or in mixtures, as defined above.

[0045] Particularly, when the composition comprises a mixture of prothioconazole and tebuconazole, the proportion of prothioconazole in the composition is advantageously from about 5 %w/w to about 20 % w/w and the proportion of tebuconazole in the composition is from about 1 %w/w to about 20 % w/w. In a preferred embodiment, the proportion of prothioconazole in the composition is from about 8 %w/w to about 16 %w/w prothioconazole and the proportion of tebuconazole in the composition is from about 8 %w/w to about 16 %w/w.

In embodiments wherein the composition comprises an azole fungicide, alone or in mixtures as defined above, and one or more non-azole fungicidal active ingredients defined above, the total proportion of the non-azole fungicidal active ingredient in the composition may be between about 5 %w/w to about 35 %w/w of the total composition, particularly from 7.5 %w/w to 30% w/w, and more particularly from 10% w/w to 20% w/w.

[0046] In a preferred embodiment, the proportion of at least one fatty acid amide in the composition of the present technology is between about 20 %w/w to about 90 %w/w of the total composition, particularly from 25 %w/w to 75% w/w, more particularly from 25 % w/w to 60% w/w, and preferably from 40 %w/w to 60% w/w. .

[0047] In some embodiments, the composition of the present technology may further comprise at least one additive selected from emulsifiers, defoamers, thickeners, dispersants, stabilizers, suspending agents, adjuvants, preservatives, polymers, acids, bases, dyes, antifreezes, biocides, fillers, wetting agents, solvents and water.

[0048] Non-limiting examples of non-ionic emulsifiers suitable for the composition of the present technology include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers (e.g., polyoxyethylene oleyl ether), polyoxyalkylene alkyl aryl ethers such as polyoxyethylene alkyl phenol, a polyoxyalkylene alkyl aryl ether/formaldehyde condensate, polyoxyalkylene aryl ether, polyoxyalkylene alkyl ester, polyoxyalkylene alkyl sorbitol ester, polyoxyalkylene sorbitan ester, polyoxyalkylene alkyl glycerol ester, polyoxyalkylene block copolymers (e.g., those containing a polyoxypropylene group), polyoxyalkylene block copolymer alkyl glycerol ester, polyoxyalkylene alkyl sulfonamide, polyoxyalkylene rosin ester, alkyl glycoside, alkyl polyglycoside, polyoxyalkylene alkyl polyglycoside, and mixtures of two or more of these.. Particular preference is given to tristyrylphenol alkoxylates and fatty acid polyglycol ether esters. Very particular preference is given to tristyrylphenol ethoxylates, tristyrylphenol ethoxy propoxylates and castor oil polyglycol ether esters, in each case individually or in mixtures. In some embodiments, the non-ionic emulsifier may be any one or more of Emulsogen EL-300 and Soprophor® 796/P.

[0049] Non-limiting examples of anionic surfactants are available in the form of an aqueous solution or in a solid state, and examples of such anionic surfactants include mono- and di-alkyl naphthalene sodium sulfonate, sodium a-olefmsulfonate, sodium alkanesulfanate, alkyl sulfosuccinate, alkylsulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkyl aryl ether sulfate, polyoxyalkylene styryl phenyl ether sulfate, mono- and dialkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl naphthalene sulfonate-formaldehyde condensates, alkyldiphenyl ether sulfonate, olefmic sulfonate, mono- and dialkylphosphate, polyoxyalkylene mono- and di-alkylphosphate, polyoxyalkylene mono- and di-phenyl ether phosphate, polyoxyalkylene mono- and di-alkyl phenyl ether phosphate, polycarboxylate, linear and branched alkylamide polyoxyalkylene ether carboxylic acid or salts thereof, alkyl polyoxyalkylene ether carboxylates, alkenyl polyoxyalkylene ether carboxylates, aliphatic acids or salts thereof, e.g., capric acid and salts thereof, lauric acid and salts thereof, stearic acid and salts thereof, oleic acid and salts thereof, N-methyl fatty acid taurides, and mixtures of two or more of these (including salts such as sodium, potassium, ammonium and amine salts). Examples are Solvesso® 200, calcium dodecylbenzenesulphonate such as Rhodocal® 70/B (Rhodia), Phenyl sulfonate CA100 (Clariant GmbH) or isopropyl ammonium dodecylbenzenesulphonates such as Atlox® 3300B (Uniqema). In some embodiments, the emulsifier may also act as a dispersant and/or wetting agent. In some implementation of this embodiment the emulsifier is Soprophor 796/P.

[0050] Additional suitable additives for the composition of the present invention include defoamers. Suitable defoamers are all substances which can typically be used for this purpose in agrochemicals. Preference is given to silicone oils, silicone oil formulations, magnesium stearate, phosphinic acids and phosphonic acids. Examples are Silcolapse® 482 from Bluestar Silicones, Silfoam® SC1132 from Wacker [dimethylsiloxanes and -silicones, CAS No. 63148- 62-9], SAG 1538 or SAG 1572 from Momentive [dimethylsiloxanes and -silicones, CAS-Nr. 63148-62-9] or Fluowet® PL 80.

[0051] In some embodiments, any one or more of the substances listed above may additionally act as a dispersant, wetting, or suspending agent. Non-limiting examples of such substances include non-ionic phenol ethoxylates such as Soprophor 796/P and Genapol ID 60. Alternatively, additional dispersant, defoamer, wetting, and suspending agent may be incorporated in the composition of the present technology. Suitable substances are all of those which can typically be used for this purpose in agrochemicals, and are well-known in the arts. [0052] In other embodiment, the composition of the present technology may comprise surfactants or esters of fatty acids. Non-limiting examples of surfactants suitable for the composition of the present technology include Plurafac SL-42, Lutensol XL-40, Ecosurf EH-3, Surfonic PEA-25, X-AES, Alfoterra 123-4S, Marlowet 4561, sodium lauryl ether sulfate, ethoxylated alcohol surfactants (e.g. , Tomadol 25-3, Tomadol 25-7), fatty acid diethanolamine (e.g., cocamide DEA), orange oil emulsifier (e.g. , Videt ME-80), acrylate-based emulsion copolymer (e.g. , Alcogum SL-70), polyoxyethers of lauryl alcohol (e.g., Laureth-7), linear isopropylamine dodecylbenzene sulfonate (e.g., Rhodocal IP AM), blended alcohol ethoxylate (e.g., Videt Q3), alkoxylated alcohol (e.g. , Tergitol 15-S-7), sodium iminodipropionate (e.g., Amphoteric 400), nonionic alcohol ethoxylates (e.g., Ecosurf EH-6), a palm kernel alcohol ethoxylated and propoxylated surfactant (e.g. , Ecosurf SA-7), sodium xylene sulfonate (e.g., Alkatrope SXS-40), or mixtures thereof. Optionally, the surfactant may be biodegradable. [0053] In a particular embodiment, the composition of the invention comprises at least an azole fungicide 5 to 30 %w/w particularly prothioconazole (alone or with tebuconazole), R1-CO-NR2R3, particularly amide of tall oil 20 to 60 % w/w emulsifier, particularly castor oil ethoxylate 10 to 30 %w/w emulsifier, particularly non-ionic fatty alcohol alkoxylates 2 to 10 % w/w [0054] From another aspect, the present technology relates to an emulsion obtainable by mixing the composition described herein with a diluent. In some embodiments, the diluent may be water. The composition of the present technology can be diluted such that the final concentration of azole fungicide, alone or in mixtures as described above, in the emulsion would be between about 0.25 g/L and about 3g/L, between about 0. 5g/L and about 2.5g/L, between about 0.75g/L and about 2.25g/L, between about 0.75g/L and about 2.15 g/L.

[0055] From another aspect, the present technology relates to an emulsion obtainable by mixing extemporaneously and separately the components of the composition described herein with the diluent. The proportions of the components and the diluent are such that the same amount of azole fungicides and amide of formula R1-CO-NR2R3, particularly amide of tall oil, are present in the emulsion as defined above.

[0056] From yet another aspect, the present technology relates to a method for improving the penetration of at least one azole fungicide into a plant comprising applying any one or more of various embodiments of the composition or emulsion described herein to said plant by spraying, painting or direct application on the leaves using a dropper, and the like.

[0057] From a further aspect, the present technology relates to the use of any one or more of embodiments of the composition or emulsion described herein in the protection or treatment of a plant in need thereof. Plants which can be protected or treated with the composition of the present technology include but are not limited to cereals such as wheat, barley, rye, oats, millet, rice, cassava and maize, or crops of peanuts, sugar beet, cotton, soybeans, oilseed rape, potatoes, tomatoes, peas and other vegetables, useful plants and ornamental plants in gardens and forests; and genetically modified varieties of each of these plants, and the seeds of these plants.

[0058] In other embodiments, the treatment may be applied separately or together with one or more other agrochemical active substances. Non-limiting examples of agrochemical active substances include but are not limited to bactericides, insecticides, acaridices, nematicides, herbicides, as well as other fungicides different from azole fungicides particularly those defined above.

[0059] In instances where the one or more other agrochemical active substances are applied together, the one or more agrochemical active substance may be added to the emulsion as described above. As such, in some embodiments, the present technology further comprises a tank mix comprising the composition of the invention with a diluent and at least one other agrochemical active substances.

[0060] In some embodiments the composition or emulsion of the present technology may be applied as an aqueous spray mixture on the leaves of the plant but may also be applied to the seed, the soil, any area and environment in which plants grow or could grow, and/or materials, plants, seeds, soil, surfaces, and/or spaces which are to be protected from attack or infestation by one or more fungus that are harmful to plants.

[0061] In some embodiments the invention also comprises a method for protecting or treating a plant in need thereof, particularly for controlling fungal infection in said plant, comprising the steps of (i) preparing a tank mix comprising at least one azole fungicide, alone or in a mixture with another azole fungicide, and at least one fatty acid amide of formula R1-CO-NR2R3, optionally adding at least another pest control agent, particularly another non-azole fungicide, and a solvent, and (ii) applying the tank mix to the plants.

[0062] The azole fungicides, their mixtures, fatty acid amides, other pest control agents, solvents and proportion thereof are as defined above in all their combinations.

[0063] Azole fungicide(s), fatty acid amide(s), solvent and optional other pest control agent may be added in any suitable order for the preparation of the tank mix. In one embodiment, the tank mix is prepared in adding a composition of the invention to the solvent. In another embodiment, the tank mix is prepared in adding the azole fungicide to a mixture of solvent and fatty acid amide. In a further embodiment the tank mix is prepared in adding the fatty acid amide to a mixture of solvent and azole fungicide. Etc.

EXAMPLES

Example 1: Preparation of prothioconazole containing emulsifiable concentrate formulations

[0064] Compositions were prepared by mixing 250 g of Prothioconazole, with a mixture of castor oil ethoxylate, polydimethylsiloxane, and DMAD comprising N,N-dimethylamides of tail-oil fatty acids (CAS: 68308-74-7) and alcohol ethoxylate or N,N-dimethyldecanamide (CAS No. 14433-76-2) and alcohol ethoxylate respectively (Table 3). The mixtures were stirred until all the Prothioconazole was dissolved and a clear solution was obtained.

[0065] In some compositions, where indicated, DMATO was replaced by DMAD. DMAD is a 9:1 mixture of N,N-dimethylamides of tail-oil fatty acids (EC: 269-665-4, CAS: 68308-74-7), and Alcohols (C9-11-iso-, C10-rich, ethoxylated, CAS: 78330-20-8).

Table 3 Preparation of E597A and E593B

[0066] Other compositions were prepared by mixing additional azole fungicides and other additives in the composition. Detailed recipes for these compositions are shown in Table 4.

Table 4 Preparation of E597B and E 597C

Example 2: Leaf cuticle preparations

[0067] The penetration of active compounds was measured in enzymatically isolated cuticles of apple tree leaves.

[0068] Fully developed leaves were cut from apple trees of the Golden Delicious ( Mains domestica) variety. Isolated adaxial astomatous leaf cuticles were further used for testing.

[0069] Next, the thus obtained cuticle for membrane transport investigations diffusion cells (= transport chambers) were placed in stainless steel. The diffusion cells were filled with an aqueous phospholipid solution (PSL).

[0070] To determine penetration, 6μL of a spray liquor of the compositions presented in Example 1 were applied to the outer side of a cuticle. Compositions were diluted in water in each case. After application, the water in the spray liquor was allowed to evaporate, and the chambers were inverted and placed in thermostated troughs, with air being blown at a defined temperature of 25 ° C and relative humidity of 75% to the outside of the cuticle. Example 3: Active leaf cuticle penetration test of radiolabelled compositions comprising tail-oil fatty acid dimethylamides, and comparison with equivalent compositions comprising N,N-dimethyldecanamide.

[0071] This study determined the penetration/diffusion of four radiolabelled prothioconazole treatments through the isolated adaxial cuticles of Golden Delicious apple leaves, over a 48 h period.

Materials and Methods

[0072] The study was conducted on astomatous leaf cuticles, enzymatically isolated from Golden Delicious apple ( Malus domestica) foliage. The cuticles were mounted, checked under magnification prior to use to establish the outer surface and to check for damage.

[0073] The composition E593B and E597A (as described in Table 3) were used at 1 g/L of active ingredient (a.i.), and E597B and E597C (as described in Table 4) used at 0.5 g/L a.i.. Radiolabelled 14C-prothioconazole was obtained from Izotop, Budapest, Hungary. Radiolabel incorporation and solution homogeneity were confirmed by sampling multiple aliquots and quantifying radioactivity prior to use. The radioactive mass constituted approx. 10% of the total a.i. in solution.

[0074] Prothioconazole penetration was studied after applying the radio labelled treatments to the outer surface of cuticles and measuring their appearance in a receiver solution in contact with the inner surface. Treatments E593B and E597A were compared together in a single study; treatments E597B and E597C were then compared in a second study. Treatments were applied to dry cuticles and left to dry before the penetration chambers were inverted. A syringe was used to fill the chambers through the sampling port. The ports were sealed, and the chambers were transported to a controlled environment and agitated gently and continuously on an orbital shaker for 48 h. The quantity of radiolabelled prothioconazole applied to cuticles in each treatment was determined by dispensing the standard application volume directly into scintillation vials at the time of treatment.

[0075] The receiver solution was sampled at six-time intervals after the solution was added; at 0, 3, 6, 9, 24 and 48 h after treatment. At each sampling period, an aliquot of the receiver solution was withdrawn quantitatively and replaced by fresh PSL. Radioactivity in the sampled receiver solution was determined by adding scintillant cocktail to each sample and assaying using a liquid scintillation counter. At the end of the experiment, the exposed cuticles were sampled and stored frozen in case needed to determine residual radioactivity associated with the cuticle. The amount of prothioconazole from each treatment penetrating at time intervals was calculated by summation, as a percentage of the total radiolabelled fungicide applied. Experiments were subjected to analysis of variance and least significant difference tests were used to compare treatments. Stabilising transformations were performed as necessary, prior to analysis.

[0076] The sample size was 10 cuticles per treatment, but cuticle failures due to fragility and breakage during the studies reduced this to 8-9 replicates per treatment.

Results

[0077] In Study 1, penetration of prothioconazole was faster and greater from treatment E593B comprising tall oil fatty acid dimethylamides than from E597A comprising N,N- dimethyldecanamide (Table 5). Both were applied at ca 1.1 g/L a.i. Similarly, in Study 2 treatment E597C comprising tall oil fatty acid dimethylamides penetrated faster and to a greater degree than E597B, when both were applied at ca 0.55 g/L. Table 5 presents the data from both studies analysed separately. The penetration time courses for Studies 1 & 2 are graphed in FIG. 1 and FIG. 2.

[0078] Analysis of all treatments as a single study confirmed no differences between % penetration of treatments E593B and E597C despite their different concentrations (P<0.0001). Penetration of these treatments was approximately twice that of the E597A and E597B.

Table 5 The % penetration of radiolabelled prothioconazole through leaf cuticle membranes

[0079] As seen in Table 5, the presence of tall oil fatty acid amides (E593B, E597C) leads to a significant increase in penetration compared to the formulations in which the dimethyldecanamide (E597A, E597B) is present. The difference between comparable formulations is statistically significant, as seen in FIG. 1 and FIG. 2.

Conclusions [0080] The four treatments tested, in this study investigating their penetration through isolated cuticles, showed significant differences in performance. Two treatments, E593B and E597C comprising tall oil fatty acid dimethylamides penetrated similarly, diffusing at a greater speed and in higher quantity than treatments, E597A and E597B comprising N,N- dimethyldecanamide.

Example 4: Preparation of prothioconazole containing emulsifiable concentrate formulations

[0081] Compositions were prepared by mixing 250 g of Prothioconazole, with a mixture of tristyrylphenol ethoxylate, ethylenediamine alkoxylate, alcohols ethoxylated propoxylated, a tristyrylphenol ethoxylate propoxylate and DMAD comprising N,N-dimethylamides of tail-oil fatty acids (CAS: 68308-74-7) and alcohol ethoxylate or N,N-dimethyldecanamide (CAS No. 14433-76-2) and alcohol ethoxylate respectively (Table 6). The mixtures were stirred until all the Prothioconazole was dissolved and a clear solution was obtained. Table 6 Preparation of E600C and E600D

Example 5: Plant uptake test of compositions comprising tail-oil fatty acid dimethylamides, and comparison with equivalent compositions comprising N,N, dimethyldecanamide. [0082] Winter barley plants were cultivated under glass, ensuring applied treatments would not conflict with the active substance to be measured. The plants were transported to the test site, watered and allowed to recover for 24 hours before application. The average height of the plants was around 30 cm with 3 or more tillers. The spray boom was set up to ensure an application from a height of 0.5 m above the plant canopy. Each composition was applied using three conventional flat fan nozzles which were mounted on a boom, attached to a track sprayer. Leaf surfaces were completely dry at the time of application. The application parameters used in this study are detailed in Table 7.

Table 7 Application parameters

[0083] Plants were arranged in rows of 3 plants across the boom width, with up to 6 rows for one application. Each composition was mixed immediately prior to application using CIPAC D water. The compositions were thoroughly combined with the water using a magnetic stirrer before transferring to the Cornelius can for application. Care was also taken to thoroughly wash the Cornelius canisters and spray lines between each composition used to prevent cross contamination. Samples of the tank mix were taken from the nozzle and stored in case required for confirmation of concentration.

[0084] Following application each set of plants was allowed to dry before destructively sampling the plants at each of the 5 timings. The relative amount of a.i. taken up into the plant at each timing was assessed by: I) extraction of material deposited on the external plant surfaces into a solvent mixture; and II) measurement of the active substance within the remaining plant material.

[0085] The environmental conditions were monitored throughout the 48-hour period following application. Measurements included temperature, humidity and spot readings of light levels. The plants were positioned indoors in a light and well-ventilated area to enable the plants to continue its natural metabolic processes. [0086] The % uptake of prothioconazole in the plant measured as the % Desthio- prothioconazole in the plant as a percentage of total amount sprayed at t=0. Table 8 demonstrates that the composition comprising tall oil fatty acid dimethylamides had a significantly higher % Desthio in the plant (FIG. 3). The difference was statistically significant. Table 8 Comparison of % Desthio in plants treated with E600C and E600D

Example 6: Plant uptake test of compositions comprising tail-oil fatty acid dimethylamides, and comparison with equivalent compositions comprising N,N- dimethyldecanamide. [0087] This study determined the comparative uptake of two radiolabelled prothioconazole treatments, into barley ( Hordeum vulgare ) foliage, over a 48 h period.

Methods and Materials

[0088] Barley seeds (Hordeum vulgare) were germinated and grown individually in pots in a controlled environment simulating spring conditions to the stage of tiller formation. They were treated at approximately 4 weeks old. [0089] Two prothioconazole formulations were assessed, E600C and E600D (all 250 g/L prothioconazole) used at 1 g/L a.i. (0.8 kg formulation/200 L/ha application).

[0090] Radiolabelled 14C-prothioconazole was obtained from Izotop, Budapest, Hungary. Radiolabelled prothioconazole in acetonitrile was dispensed into micro-vials and blown down to dryness. Prothioconazole treatments were pre-warmed in a water bath, appropriate aliquots of each formulation were added on top of the radiolabelled a.i. and the micro-vial contents were sonicated. Appropriate water volumes were then added to the micro-vials to dilute each treatment to the required concentration (0.8 kg/200 L). Radiolabel incorporation and solution homogeneity were confirmed by sampling multiple aliquots and quantifying radioactivity prior to use. [0091] Treatments were applied to the central region on the adaxial surface of the youngest fully expanded leaf on each plant (5 replicates per treatment). Droplets (30x0.24 μl) were applied by micro syringe with a repeating dispenser, simulating an application volume of 200 L/ha (2 μl/cm²). The quantity of radiolabelled prothioconazole applied to replicate leaves in each treatment was determined by dispensing the standard application volume directly into scintillation vials (4 replicates) at the time of treatment. Plants were allocated to treatments using a completely randomised design.

[0092] Uptake of radiolabel into the plant was determined at five intervals after treatment; 0, 3, 6, 24 and 48 h. This was assessed by washing the treated leaf to recover unabsorbed radiolabel. The washings were taken up in ACS scintillant solution and the radioactivity quantified by liquid scintillation counting. The 0 h recovery was performed at 10 mins after treatment and recovered > 99% of applied radioactivity for all treatments.

[0093] The % uptake of prothioconazole in the plant was measured as described in Example 6. Table 8 demonstrates that the composition comprising tall oil fatty acid dimethylamides (E600D) had a significantly higher % uptake in the plant than the compositions (FIG. 4). The difference was statistically significant. Table 8 Comparison of % uptake in plants treated with E600C and E600D

[0094] Variations and modifications will occur to those of skill in the art after reviewing this disclosure. The disclosed features may be implemented, in any combination and sub combinations (including multiple dependent combinations and sub-combinations), with one or more other features described herein. The various features described or illustrated above, including any components thereof, may be combined or integrated in other systems. Moreover, certain features may be omitted or not implemented. Examples of changes, substitutions, and alterations are ascertainable by one skilled in the art and could be made without departing from the scope of the information disclosed herein. [0095] It should be appreciated that the invention is not limited to the particular embodiments described and illustrated herein but includes all modifications and variations falling within the scope of the invention as defined in the appended claims.

Claims

1. A composition comprising:

At least one azole fungicide, and At least one fatty acid amide of formula R1-CO-NR2R3, wherein R1 is a fatty acid derived from a vegetable oil, and R2 and R3 are independently a methyl or an ethyl.

2. The composition of claim 1, wherein the at least one azole fungicide is selected from the group consisting of tebuconazole, triadimenol, triadimefon, epoxiconazole, metconazole, fluquinconazole, cyproconazole, penconazole, ipfentrifluconazole, mefentrifluconazole and prothioconazole.

3. The composition of claim 2, wherein at least one azole fungicide is prothioconazole.

4. The composition of one of claims 1 to 3, wherein the fatty acid amide is derived from a vegetable oil selected from the group consisting of coconut, corn, cottonseed, palm, soybean and tall oil.

5. The composition of claim 4, wherein the vegetable oil is tall oil.

6. The composition of any one of claims 1 to 5, wherein the fatty acid derived from a vegetable oil comprises at least one Laurie, Myristic, Palmitic, Stearic, Lauroleic, Myristoleic, palmitoleic, Oleic, and Linoleic acid.

7. The composition of any one of claims 1-6, wherein the proportion of the at least one azole fungicide to the fatty acid amide is between about 1 : 1 to about 1:15.

8. The composition of any one of claims 1-7, wherein a proportion of at least one fungicide in the composition is between about 4 %w/w to about 60 %w/w.

9. The composition of any one of claims 1-8, wherein a proportion of the at least one fatty acid amide in the composition is between about 20 %w/w to about 90 %w/w.

10. The composition of any one of claims 1-9, wherein the at least one azole fungicide comprises at least a first azole fungicide and a second azole fungicide.

11. The composition of any one of claims 1-10, wherein the proportion of the first azole fungicide to the second azole fungicide is between about 10: 1 to about 1:10.

12. The composition of any one of claims 1-11, wherein the proportion of the first azole fungicide to the second azole fungicide is 1:1.

13. The composition of any one of claims 10-12, wherein the first azole fungicide is prothioconazole.

14. The composition of claim 13, wherein the proportion of prothioconazole to the second azole fungicide is between about 3 : 1 to about 1 :2.

15. The composition of any one of claims 10-14, the second azole fungicide is tebuconazole.

16. The composition of claim 15 when dependent on claim 13 or 14, wherein the proportion of the prothioconazole in the composition is from about 5 %w/w to about 20 % w/w and the proportion of tebuconazole in the composition is from about 1 %w/w to about 20 % w/w.

17. The composition of claim 16, wherein the proportion of the prothioconazole in the composition is from about 8 %w/w to 16 %w/w, and the proportion of tebuconazole in the composition is from about 8 %w/w to 16 %w/w tebuconazole.

18. An emulsion obtainable by mixing the composition of any one of claims 1-9, with a diluent.

19. The emulsion of claim 18, wherein the diluent is water.

20. The emulsion of claim 18 or claim 19, wherein the concentration of the at least one azole fungicide is between about 0.25 g/L and between about 1.5g/L.

21. A method for improving the penetration of at least one azole fungicide into a plant comprising applying any one or more of the composition of any one of claims 1-17, and the emulsion of any one of claims 18-20, to said plant.

22. The method of claim 21, wherein said composition or emulsion is applied as an aqueous spray mixture.

23. Use of any one or more of the composition of any one of claims 1-17, and the emulsion of any one of claims 18-20, in the protection or treatment of a plant in need thereof.

24. A method for controlling one or more harmful fungus comprising contacting the harmful fungus, a habitat thereof, a host thereof, optionally plants, and/or seed, and/or soil, an area and an environment in which plants grow or could grow, and/or materials, plants, seeds, soil, surfaces, and/or spaces which are to be protected from attack or infestation by one or more fungus that are harmful to plants, with an effective amount of any one or more of the composition according to any one of claims 1-17 or the emulsion of any of claims 18-20.