IL308593A - Reducing the environmental impact of antifungal amplification - Google Patents

Description

REDUCING ENVIRONMENTAL IMPACT OF FUNGICIDAL ENHANCEMENT Throughout this application, various publications are cited. Disclosures of the documents and publications referred to herein are hereby incorporated in their entireties by reference into this application.

Field of the Present Subject Matter The present invention relates to fungicidal combinations comprising at least two components: (1) polyphenol-based component and (2) at least one pesticidal, such as a fungicide, component selected from the group of N3-substituted-N1-sulphonyl-5-fluoropyrimidine compounds and/or derivatives as disclosed and defined in US Patent application 13/090,616, and in particular 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one represented by the following structure, The combinations are more effective for treating a plant or soil against fungal and/or bacterial disease than if each fungicidal component in the combination, at the same amount is applied alone.

The polyphenol based components are typically more environmentally innocuous or safe than many pesticidal enhancement agents, relatively, and thus they may in some cases be seen as an environmental alternative to other less environmentally safe pesticidal enhancement agents, such as fungicidal enhancement agent, such as fungicidal N3-substituted-N1-sulphonyl-5-fluoropyrimidine compounds and/or their derivatives. However, inventors are aware that some useful polyphenol compounds do indeed have unwanted effects in high amounts, practitioners are thus cautioned to limit the use of the polyphenol compounds at least initially during optimization to evaluate if any untoward undesirable effects are seen above an amount sufficient to provide the inventive advantages and not to ignore their common sense when employing particular polyphenol compounds that might have known unwanted consequences. To be clear, it is generally advised to initially test the effect of different combination contents as a ranging exercise when a polyphenol compound is first used for the enhancement of 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, such as 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one for the first time.

The most typical component (2) fungicide is known by various names and identifiers used interchangeably throughout this disclosure, partly to signify that in the majority of cases the choice of label is immaterial as the compound remains the important feature.

The fungicidal combinations of the inventions can, in certain embodiments further comprise one or more additional pesticides as component (3), chosen from herbicides, fungicides, insecticides and other known classes of pesticides.

The combination of Polyphenol compounds (1) and 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides (2) is more effective for treating a plant or soil against fungal and/or bacterial disease than if each component in the combination, at the same amount is applied alone. The invention enables reducing the additional fungicides used together with fungicides of component (2) or even eliminate the need for their use, often resulting in equivalent or superior fungicidal activity or performance.

Clearly, the invention thus also relates to several advantages obtainable by the use of polyphenol-based compounds, to increase plant health and to enhance the performance of 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, such as 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one represented by the following structure, . The combination of 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides and optionally additional pesticides such as fungicides are noted for their enhanced performance, and the inclusion of polyphenol compounds enables the reduction of the amount of both the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides and often any pesticidal compounds combined with them.

Uses of N3-substituted-N1-sulfonyl-5-fluoropyrimidinone derivatives as fungicides were described in U.S. Patent No. 8,263,603, issued September 11, 2012, the content of which is incorporated herein by reference in its entirety. Methods of preparation of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one were described in U.S. Patent No. 9,850,215, issued December 26, 2017 and U.S. Patent No. 9,840,476, issued December 12, 2017, the contents of each of which are incorporated herein by reference in their entirety.

U.S. Patent No. 8,263,603 also described fungicidal compositions for the control or prevention of fungal attack comprising N3-substituted-N1-sulfonyl-5-fluoropyrimidinone derivatives and a phytologically acceptable carrier material, and methods of use thereof.

Use of 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-ones as seed treatment to prevent or control plant disease was described U.S. Patent Application Publication No. 2018/0000082, published on January 4, 2018.

Synergistic mixtures comprising 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one and at least one fungicidal sterol biosynthesis inhibitor were described in U.S. Patent No. 9,526,245, issued December 27, 2016 and U.S. Patent No. 10,045,533, issued August 14, 2018.

Synergistic mixtures comprising 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one and at least one succinate dehydrogenase inhibitor were described in U.S. Patent No. 9,532,570, issued January 3, 2017 and U.S. Patent No. 10,045,534, issued August 14, 2018.

While the use of polyphenol-based compounds alone, is found to increase the performance of control and increase plant health, additional advantages are available when the polyphenol-based compounds are optionally used in combination with even minimal amounts of other performance enhancing ingredients.

Methods for enhancing performance, controlling, treating, or preventing fungal and/or bacterial diseases in crop plants are also disclosed utilizing the combinations of the invention which methods are an integral part of the invention.

Background of the Invention Fungicides as herein defined, are compounds of natural or synthetic origin which act to protect plants against damage caused by fungi and/or bacteria. In spite of the benefits derived from the use of fungicides in agriculture such as protection of crops and improved productivity, it is nowadays desirable to reduce the amount of fungicides used in the fields owing to the potential health risks associated with an intensive use of agrochemicals. It would be of benefit to the environment to reduce the amount of fungicides used, even if they are as innocuous and safe as 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one. Inventors foresee that the improvement in fungicidal performance of 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-one fungicides by combining them with polyphenol compounds will inter alia allow for lower amounts of the fungicides, which will clearly have environmental benefits.

By using polyphenol compounds especially those sourced or derived from natural sources, plants, trees, algae etc. to enhance fungicidal activity of a fungicide, the amounts of polyphenol compound that can be included in the inventive combinations with 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one to enhance fungicidal performance is not generally limited due to environmental damage or exposure, and gives greater scope for enhancement than would be possible if the "enhancement agent" was a pesticide or other fungicide having a limit as to its use due to environmental concerns.

In particular it would be desirable to reduce the amounts of additional pesticidal compounds that may have been considered to be combined with 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one to enhance fungicidal performance or expand the range of crops and pathogens addressed, without loss of benefit usually associated with their current use levels.

Another important issue associated with fungal and/or bacterial attacks is the concomitant loss of nutrients which leads to a decrease in the overall yield of the crop. It is likely that one of the benefits associated with combination of polyphenol compounds with 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one will avoid this loss of nutrients and improve crop yields associated at least with crop health benefits of freeing the crop plants from this type of stress.

There is therefore a need for improving the treatment or prevention of plant disease caused by pathogen that also often enables higher yields while preserving a high amount of nutrients in crops while enabling a reduction in the amounts of 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1H)-one fungicides required for fungicidal control.

This clearly provides a significant environmental advantage by reducing the amount of agrochemicals applied; however in addition, unexpected plant health benefits of application of compositions of the invention have been noted, including effects like greening, more leaf duration, more photosynthesis, and less environmental stress, to name but a few that are noted during field trials.

While it is possible that the increased fungicidal efficacy is one of the major commercial impacts of combining polyphenol compounds with 5-fluoro-4-imino-3-methyl-1-tosyl-3,dihydropyrimidin-2(1H)-one, the possible reduction of the content of fungicides without loss of efficacy or performance for example, has further surprising advantages as regards the quality of fungicidal compositions.

Summary of the Present Subject Matter The present invention provides a multi-component combination which comprises at least two components: (1) polyphenol-based component, and as component (2) at least one 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide, generally, the polyphenol-based component (1), contains naturally sourced or derived, polyphenol-based compounds.

A typical 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide for use in this invention is 5-fluoro-4-imino-3-methyl-1-tosyl-3,dihydropyrimidin-2(1H)-one represented by the following structure, .

The adaptation may be the provision of compositions of polyphenol compounds as additives for preparing spray mixes or tank mixes of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide. In some embodiments, a kit is provided comprising a packaged concentrated composition of 5-fluoro-4-imino-3-methyl-1-tosyl-3,dihydropyrimidin-2(1H)-one together with a composition of polyphenol for combination with the 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one in a water dilution just prior to application. Instructions for the useful methods of combination and dilution is often part and parcel of the adaptation.

These adapted compositions are often in the form of a kit containing packaged 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one and compositions and polyphenol compounds with packaged instructions for adaptation of the composition for specific plants and specific plant pathogens.

A typical compound of component (2) useful in combinations, mixtures, compositions etc. with the polyphenol-based compounds of component (1) is 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one (alternative nomenclature), CAS No. 1616664-98-2, though clearly fungicidally useful analogues and derivatives of this compound are contemplated.

As will be clear from the foregoing discussion, often the advantage of combining 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one fungicide (2) and polyphenol compound(s) is increased efficacy of the fungicide. Whether this enhanced efficacy is due to the hydrophobic/lipophilic balance achieved, increase in migration across biological membranes or through some other mechanism the resultant effect is what is significant and it may be immaterial why this happens though it is possible that the enhancing effects are due to a combination of such mechanisms.

The present invention also provides a multi-component combination comprising at least two components: (1) an amount of polyphenol-based component, and (2) an amount of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone, wherein the combination is more effective for treating a plant or soil against fungal and/or bacterial disease than if each component in the combination, at the same amount is applied alone.

The present invention also provides a multi-component combination, admixture etc., comprising at least two components: (1) an amount of polyphenol-based component, and (2) an amount of at least one 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide component, wherein the combination is more effective for treating a plant or soil against fungal and/or bacterial disease than if each component in the combination, at the same amount is applied alone. Often the polyphenol-based component (1), contains naturally sourced polyphenol-based compounds.

Furthermore, the present invention provides a combination comprising at least two components: Component (1) an amount of polyphenol-based component, Component (2) an amount of at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide component exemplified by a compound represented by the following structure, . The combination optionally, or advantageously further contains, one or more additional fungicides.

Polyphenol-based compound of the invention are often naturally sourced or derived from natural products, and/or the polyphenol-based compound of the invention are exemplified by a group including phenolic acids, stilbenes, lignans, hydrolyzable tannins, tannic acid, flavonoids and combination thereof, Castalagin, extracts of water-soluble tannins, and extracts of water-soluble Proanthocyanidins.

In some embodiments, flavonoids refer but are not limited to flavones, aurones, anthocyanins, leucoanthocyanidins, flavonols, flavanols, flavanones, chalcones, isoflavonoids, proanthocyanidins and combination thereof.

In some embodiments, the polyphenol-based component is comprised of one or more extracts which each comprise at least one structure/source of polyphenols.

In useful polyphenol component (1) embodiments, tannins are used which include various types of tannins, such as condensed and/or hydrolyzable tannins, and/or phlorotannins. Noted are, condensed tannins of the procyanidin and/or prodelphinidin type, such as of maritime pine (Pinus pinaster), of Chilean pine (Araucaria Araucana), of Pecan nuts (pecan) , of Spruce (Picea abies) , of Douglas, of fir etc,. and/or condensed tannins of the prorobinetinidin and/or profisetinidin type, such as of Mimosa (Acacia mearnsii, Acacia mollissima, Acacia mangium, Acacia catechu) , of Quebracho Schinopsis lorentzii, Schinopsis balansae) , of Gambier Uncaria gambir) , etc,. and/or hydrolysable tannins, such as of chestnut (Castanea sativa, Castanea vesca) , of Tara Caesalpinia spinosa) , etc,. and/or -phlorotannins extracted from algae.

These tannins can be possibly employed also in their form purified by extraction with organic solvents, through processes such as acylation, methylation, ethoxylation, propoxylation, etc., and/or in their form modified or transformed by means of various chemical and physical reactions, such as polymerization, oxidation or enzymatic or chemical hydrolysis, and/or with the introduction of amino groups, so that the tannins can also be in the form of sulphited, sulphonated, oxidized, acetylated, esterified, ethoxylated or propoxylated substances, or possible mixtures thereof.

Noted are the polyphenol including, Flavonoids such as Anthocyanins, Chalcones, Dihydrochalcones, Dihydroflavonols, Flavanols, Flavanones, Flavones, Flavonols, and Isoflavonoids; Lignans; Alkylmethoxyphenols; Alkylphenols; Curcuminoids; Furanocoumarins; Hydroxybenzaldehydes; Hydroxybenzoketones; Hydroxycinnamaldehydes; Hydroxycoumarins; Hydroxyphenylpropenes; Methoxyphenols; Naphtoquinones; Phenolic terpenes; Tyrosols; Phenolic acids such as Hydroxybenzoic acids, Hydroxycinnamic acids, Hydroxyphenylacetic acids, Hydroxyphenylpentanoic acids and Hydroxyphenylpropanoic acids; and Stilbenes (phytoalexins).

Also noted are, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid 1700MW, and Resveratrol.

Further, the present invention also provides combinations wherein the amount of polyphenol-based component (1) and the amount of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide of component (2), if applied together is more effective for treating or protecting plants or soil against fungal and/or bacterial infection than if each component at the same amount is applied alone, and wherein the amounts of additional fungicidal component compounds when present, are reduced (or may be reduced without deleterious effect), as compared to comparable fungicidal combinations comprising the same amount of the fungicide of component (2), where the polyphenol-based component (1) is absent.

To be clear though, the addition of superfluous types of pesticidally active ingredients, or amounts thereof which are superfluous to requirements, or to combinations of the inventions will not remove the combinations from the envisioned scope of the invention. In general, it is desired to reduce the overall amount of applied pesticides and if redundant it is wasteful to include them.

By using relatively environmentally safe polyphenol compounds especially those sourced or derived from natural sources, plants, trees, algae etc. to enhance fungicidal activity of a N3-substituted-N1-sulphonyl-5-fluoropyrimidine compounds such as 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one fungicide, the amounts of polyphenol compound that can be included in the inventive combinations with 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one to enhance fungicidal efficacy is not generally as severely limited due to environmental damage or exposure, and gives greater scope for enhancement than would be possible if the "efficacy enhancement agent" was a pesticide or other fungicide having a limit as to its use due to environmental concerns.

In several embodiments of the invention, the inventive combination comprises a mixture of the polyphenol-based component (1) with a separately prepared component (2) composition or admixture comprising a fungicide compound represented by the following structure, .

Polyphenol-based compounds of the invention are exemplified by a group including phenolic acids, stilbenes, lignans, hydrolyzable tannins, tannic acid, flavonoids and combination thereof. Castalagin; extracts of water-soluble tannins; and extracts of water-soluble Proanthocyanidins.

In some embodiments, flavonoids include but are not limited to flavones, aurones, anthocyanins, leucoanthocyanidins, flavonols, flavanols, flavanones, chalcones, isoflavonoids, proanthocyanidins and combination thereof are used.

To a very large degree the polyphenol compounds employed in this invention as fungicidal efficacy enhancing agents for 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one fungicide are environmentally safe and thus may be used freely. So, while another known particular synthetic fungicide may have been previously shown to enhance the efficacy of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one as a fungicide, it should be clear that the environmentally safe polyphenol compounds have the advantage of not being limited by their environmental impact and can often be included freely. Thus, even if one synthetic chemical is a very "potent" efficacy enhancement agent for 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one, it may well be environmentally beneficial to replace that efficacy enhancement agent at least partially, with the inventive polyphenol compounds even if the enhancement achievable per gram of the compound is lower in absolute terms.

The invention also includes as an embodiment, the mixture of component (1) with additional fungicide component alone, but especially adapted for use in combination with one or more component (2) 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, for example as part of a kit, or otherwise adapted for use for combining with one or more component (2) 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides to prepare the three-component embodiments of the inventive combinations.

As should be clear now it is the combination of the 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone component (2) with the polyphenol compound component (1) that is significant rather than necessarily any other components in a composition comprising the combination or the precise method of combination or preparation. However, inventors are well aware that the use of certain additives including though not limited to surfactants emulsifiers, solvents and adjuvants as well as additional pesticidal ingredients can often be employed to optimize compositions including the inventive compositions. These optimizations are well within the skills of persons skilled in formulating agrochemical pesticide formulations. In a similar manner, methods of increasing stability both physical and chemical by addition of available ingredients are assumed to be within the common knowledge.

Detailed Description of Specific Embodiments of The Invention Definitions Prior to setting forth the present subject matter in detail, it may be helpful to provide definitions of certain terms to be used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this subject matter pertains.

Throughout the application, descriptions of various embodiments use the term "comprising"; however, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language "consisting essentially of" or "consisting of." Often when relating to a list of options, or optional choices of ingredient etc., the phrase "selected from the group consisting of" has been used in this disclosure, however, in all cases the corresponding phrases "selected from the group of" or "selected from the group comprising" is specifically intended as an option, and vice versa, unless the context requires the specific interpretation.

All disclosed lists of optional ingredients etc., should be seen as a disclosure of both closed and open lists as two independently disclosed alternatives.

The term "a" or "an" as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the terms "a," "an" or "at least one" can be used interchangeably in this application, to be clear that the use of terms "a," or "an" does not intend to convey the absence of multiples unless the context requires it.

For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term "about". Unless the context clearly establishes otherwise a variance of ±10% in the value of a number should be assumed by the term about. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Inventors intend to report numerical values rounded up to no more than one digit after the decimal point. While every effort has been expended to avoid the error, if a numerical value disclosed herein has been mistakenly recorded as having more than one numeral after the decimal point, it should be considered to have been an inadvertent error (unless it is a very small non-zero value), and the figure should be understood to be that value rounded up or down to a maximum of a single numeral after the decimal point, e.g., within this disclosure, a typographical error that records a figure of "147. 4821", should be understood that inventors intention was to refer to a correct value of "148", unless the context makes clear that 147.5 is required. Likewise values actually below 0.05 will of course be recorded so as to not be record a value of zero, e.g., 0.will not be rounded down to 0.0.

"About" as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system), in this respect context is important. However, unless the context makes it clear otherwise, in this regard, use of the term "about" herein specifically includes ±10% from the indicated values in the range and unless it is clear from the context, that the term "about" cannot be reasonably understood to be ±10% from the indicated value. A case in point is a "content of 95%" for an ingredient. This value is to be understood as being "about 95%", however the term 95% ±10% is nonsensical obviously the intention was thus not to include values greater than 100%.

In addition, the endpoints of all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and specifically include all intermediate points and ranges. Thus, it is understood that where a parameter range is provided, all integers within that range, and tenths thereof, are also provided by the invention, and as with all numbers, accepted principles of numerical rounding should be employed. For example, a range of "10%-50%" specifically includes 9.5%, 9.8, 10%, 10.1%, 10.2%, etc. up to 50.4%.

As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items, thus this term often replaces the use of the double alternatives of both expression x and y as well as x or y. Expressions such as "at least one of," when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.

It will be understood that when an element is referred to as being "on" another element, it may be directly in contact with the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present that may create a barrier between them.

It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present embodiments.

The terminology used herein is for the purpose of describing or illustrating particular embodiments only and is not intended to be limiting. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The term "or" means "and/or" unless the context requires otherwise. It will be further understood that the terms "comprises" and/or "comprising," or "includes" and/or "including" or "contains" and/or "containing", if used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

As used herein, the term "mixture" as regards agrochemicals, includes, but is not limited to, an assemblage of agrochemicals typically, for application either by simultaneous, contemporaneous, concomitant, sequential and/or succession/successive application.

Thus, the term "mixture" as regards components includes, inter alia, a combination in any time of application of the individual components e.g., simultaneous, contemporaneous, concomitant, and/or succession/successive application and/or in any physical form, e.g., composition, blend, admixture, solution, suspension, dispersion, emulsion, alloy, or the like. Mixture or mixing also may refer to combining and applying the active components as one composition and/or formulating each of the active component in the mixture or combination as separated compositions and application at the same time or in separated applications at the same time or different times, these mixture of components can be provided in a kit, or otherwise adapted for combination according to the invention.

As used herein, the term "simultaneous" if used in connection with application of agrochemicals means that the agrochemicals (of the mixture) are applied in an admixture, for example, a tank mix. For simultaneous application, the combination (mixture), may be the admixture itself, or separate containers each containing an agrochemical component or mixture of some components that are combined prior to application, typically provided as a kit, or otherwise adapted for end-use combination.

As used herein, the term "contemporaneous" if used in connection with application of agrochemicals (of the mixture) means that an individual agrochemical is applied perhaps separately from another agrochemical or premixture at the same time or at times sufficiently close together that a synergistic activity or an activity that is additive or more than additive relative to the activity of either agrochemical alone at the same dose is achieved.

As used herein, the term "succession" or "successive" if used in connection with the application of agrochemicals (of the combination) means that an individual agrochemical is applied at separate application starting times from another agrochemical, one after the other.

As used herein, the specific term "fungicidally effective amount" of a known active compound or component refers to an amount of the active component that is recommended for use, for example, to control the relevant fungi on the relevant crop. In some instances, however it will be clear from the context that an amount which is effective fungicidally, is a reduced though, still effective amount of an active component enabled by implementing the invention, as compared to the commercially recommended or previously recognized amount. The commercially recommended amount for each active component, often specified as application rates of the commercial formulation, may be found on the label accompanying the commercial formulation. The commercially recommended application rates of the commercial formulation may vary depending on factors such as the plant species and the fungus to be controlled.

For example, if a fungicide concentrated composition comprising 200g/L of a single fungicidal ingredient is marketed in 4 liter containers to treat a specific fungal infection of each hectare of a specific crop requiring 800g ai/ha, applying less than this recommended amount of that fungicide is considered less than its fungicidally effective amount. Similarly in the above example if the concentrate contained less than 200g a.i./L in a 4 liter preparation for 1 hectare it would be considered as containing less than its fungicidally effective amount.

In general, if application of particular amount of a specific fungicide achieves less than 70% control of a specific fungal pathogen in a specific crop (less than 70% efficacy), it is considered that that amount of that fungicide is less than a fungicidally effective amount, of course there are particularly intractable pathogens in particular crops where even 50% fungicidal efficacy is currently seen as the "gold standard" for that pathogen.

Of course, when considering intransigent or difficult to treat fungal infections, the level of control is based on the industry standard, so that if the maximum level of control achievable with a specific solo fungicide to-date for a particular fungal infection is considerably less than 80% control, the term less than a fungicidally effective amount, will be based on the amount known or understood to achieve that maximum level of control at that time with that active ingredient.

As used herein, the term "treating a plant or soil against fungal infection" includes, but is not limited to, protecting the plant or soil against fungal attack, preventing fungal infection of the plant or soil, controlling fungal disease infecting the plant or soil, and reducing fungal infection of the plant or soil.

As used herein, the term "more effective" includes, but is not limited to, increasing efficacy of fungal disease control, prolonging protection and reducing the amount of time needed to achieve a given level of fungal control, prolonging the duration of protection against fungal attack after application and extending the protection period against fungal attack and/or reducing the amount of time needed to achieve a level of fungal control compared to when each fungicide at the same amount is applied alone.

As used herein, the term "effective" if used in connection with any combination, mixture or composition may be but is not limited to any of, effective in controlling fungal disease, effective in preventing fungal disease, effective to decrease time for effectively controlling fungal disease, effective to decrease the amount of the fungicide(s) required for effectively controlling fungal disease, effective in extending the controlling effect of the individual combination, mixture and/or composition the mixture in terms of type of crop and disease, effective to prolong the time of controlling effect of the mixture compared to the individual combination, mixture and/or composition the mixture in terms of type of crop and disease, effective to prolong the time of controlling effect of the individual combination, mixture and/or composition the mixture in terms of type of crop and disease.

As used herein, the term "effective amount" typically refers to an amount of the agrochemical composition or of the mixture which is sufficient for controlling harmful fungi on crop plants and does not cause significant damage to the treated crop plants, about 80% control or more of a pathogen is generally indicative of effective control and the applied dose that achieves this is generally seen as an effective amount, with some exceptions.

As used herein, the term "agriculturally acceptable carrier" means carriers which are known and accepted in the art for the formation of compositions for agricultural or horticultural use.

As used herein, the term "adjuvant" is broadly defined as any substance that itself is not an active ingredient, but which enhances or is intended to enhance the effectiveness of the pesticide with which it is used. Adjuvants may be understood to include, but are not limited to, spreading agents, penetrants, compatibility agents, and drift retardants.

As used herein, the term "agriculturally acceptable inert additives" is defined as any substance that itself is not an active ingredient but is added to the composition such as thickening agent, sticking agents, surfactants, anti-oxidation agent, anti-foaming agents and thickeners.

As used herein, the term "tank mix" means that one or more chemical pesticides or compositions are mixed in the spray tank at the time of spray application.

As used herein, the term "ready mix" means a composition that may be applied to plants directly after dilution. The composition comprises the combination of the active ingredients.

As used herein the term "plant" or "crop" includes reference to agricultural crops including field crops (soybean, maize, wheat, rice, etc.), vegetable crops (potatoes, cabbages, etc.), fruits (peach, etc.), semi-perennial crops (sugarcane) and perennial crops (trees, coffee, guava for example).

As used herein the term "plant" or "crop" includes reference to whole plants, plant organs (e.g., leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, seedling, cutting or plant seeds. This term also encompasses plant crops such as fruits.

The term "plant" may also include the propagation material thereof, which may include all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication of the plant. It may also include spores, corms, bulbs, rhizomes, sprouts, basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination, rooting or after emergence from soil or any other kind of substrate, be it artificial or natural.

As used herein the term "propagation material" is to be understood to denote all the generative parts of the plant such as seeds and spores, vegetative structures such as bulbs, corms, tubers, rhizomes, roots stems, basal shoots, stolons, and buds.

As used herein, the term "locus" includes not only areas where fungal infection/disease may already be shown, but also areas where fungal infection/disease have yet to show and also area under cultivation. Locus includes but is not limited to soil and other plant growth medium.

As used herein, the term "locus" includes a habitat, breeding ground, plant, propagation material, soil, area, material, or environment in which a fungal disease is growing or may grow.

As used herein the term "ha" refers to hectare.

As used herein, the terms "control" or "controlling" or "treating" include but are not limited to, preventing fungal disease, protecting plants from fungal disease, delaying the onset of fungal disease, and combating or killing fungal disease. They also may include the curative and/or eradication action of compounds and compositions on underway fungal and/or bacterial diseases. Controlling fungal disease infecting the plant, propagation material of the plant or locus of the plant, controlling a plant or soil disease caused by phytopathologic fungi and/or bacteria (pathogen), controlling fungal attack on the plant or, propagation material of the plant or locus of the plant includes curative application and/or protectant/preventive application and/or persistence application to do so.

As can be seen, many functions are included in the term fungicidal performance, and not all of these functions are limited to a numerical value of eradicating a pest.

The term "applying" or "application", as used herein, includes but is not limited to applying the compounds and compositions including those of the invention, to the plant, to a site of infestation by fungi and/or bacteria, to a potential site of infestation by the fungi and/or bacteria, which may require protection from infestation, or the environment around the habitat or potential habitat of the fungi and/or bacteria. It also includes reference to the activity of compounds and compositions on plants and fungal and/or bacterial tissues with which they come into contact. The application may be by methods described in the present invention such as by spraying, dipping, etc.

As used herein the term "curative application" means, inter alia, an application of one or more compounds including fungicide for controlling fungal and/or bacterial infection of the plant or locus, wherein the fungicidal combination, mixture or composition is applied after an infection or after disease symptoms are shown, and wherein the fungal and/or bacterial infection is reduced and/or curing a plant or soil disease caused by phytopathologic/phytopathogenic fungi and/or bacteria.

As used herein, the term "curative treatment" or "curative activity" means an application of one or more pesticides, and particularly fungicidal material for controlling pest infection of the plant or locus, after an infection or after disease symptoms are shown and/or when the disease pressure is high. Disease pressure may be assessed based on the conditions associated with disease development such as spore concentration and certain environmental conditions. In some embodiments, the pest is a fungus and/or bacteria.

As used herein, the term "protectant application" means an application of one or more fungicidal combination, mixture, or composition, for preventing fungal and/or bacterial infection of the plant or locus, wherein the fungicidal combination, mixture or composition is applied before infection/disease occurs, before any disease symptoms are shown or when the disease pressure is low. Disease pressure may be assessed based on the conditions associated with disease development such as spore concentration and certain environmental conditions.

As used herein, the term "preventative treatment" or "preventative activity" means an application of one or more pesticide for controlling pest infection of the plant or locus, before an infection or before disease symptoms are shown and/or when the disease pressure is low. Disease pressure may be assessed based on the conditions associated with disease development such as spore concentration and certain environmental conditions. In some embodiments, the pest is a fungus and/or bacteria.

As used herein, the term "cultivated plants" includes plants which have been modified by breeding, mutagenesis, or genetic engineering. Genetically modified plants are plants, which their genetic material has been modified by the use of recombinant DNA techniques. Typically, one or more genes have been integrated into the genetic material of such a plant in order to improve certain properties of the plant.

The term "plant health" comprises various sorts of improvements of plants that are not connected to the control of pests. For example, advantageous properties that may be mentioned are improved crop characteristics including: emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance or improved non biotic stress mitigation (e.g. against drought, heat, salt, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), shortening of stalks, increased diameter of stalks, increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination; or any other advantages familiar to a person skilled in the art.

As used herein, the phrase "agriculturally acceptable carrier" means carriers which are known and accepted in the art for the formation of compositions for agricultural or horticultural use.

In some embodiments, the disease is fungal disease.

In some embodiments, infection is disease and/or disease caused by pathogen.

The term "enhancing crop plants" as used herein means improving one or more of plant quality, plant vigor, nutrient uptake, root system, tolerance to stress factors or improved non biotic stress mitigation, and/or yield in a plant to which the mixture or composition described herein is applied as compared to a control plant grown under the same conditions except to which the mixture or composition described herein is not applied.

The term "improving plant quality" as used herein means that one or more traits are improved qualitatively or quantitatively in a plant to which the mixture or composition described herein is applied as compared to the same trait in a control plant grown under the same conditions except to which the mixture or composition described herein is not applied. Such traits include but are not limited to improved visual appearance and composition of the plant (i.e. improved color, density, uniformity, compactness), reduced ethylene (reduced production and/or inhibition of reception), improved visual appearance and composition of harvested material (i.e. seeds, fruits, leaves, vegetables, shoot/stem/cane),), improved carbohydrate content (i.e. increased quantities of sugar and/or starch, improved sugar acid ratio, reduction of reducing sugars, increased rate of development of sugar), improved protein content, improved oil content and composition, improved nutritional value, reduction in anti-nutritional compounds, increased nutrient uptake, stronger and healthier roots, improved organoleptic properties (i.e. improved taste), improved consumer health benefits (i.e. increased levels of vitamins and antioxidants), improved post-harvest characteristics (i.e. enhanced shelf-life and/or storage stability, easier processability, easier extraction of compounds), and/or improved seed quality (i.e. for use in following seasons).

As used herein, the term "plant growth regulation" or "regulating plant growth" includes restricting vertical stem growth, promoting root growth, stunting, increasing stem diameter and stem-wall thickness, and the like.

As used herein, the term "plants" refers to any and all physical parts of a plant, including but not limited to seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

Combinations and mixtures The present invention provides combinations often referred to as multi-component combinations comprising at least two components: Component (1) an amount of polyphenol-based component, and Component (2) an amount of at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide which is most typically exemplified by, 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone.

Embodiments of the present invention provide combinations often referred to as multi-component combinations comprising at least two components: Component (1) an amount of polyphenol-based component, and Component (2) an amount of an N3-substituted-N1-sulphonyl-5-fluoropyrimidine fungicides such as 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide compound of formula I, , wherein R 1 is selected from H, C 1-C 6 alkyl, and C 1-C 6 alkoxy, and R 2 is selected from C 1-C 6 alkyl, phenyl, benzyl and -CH 3-thiophenyl.

In many preferred embodiments the fungicidal compound of component (2) is 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one represented by the following structure, .

In some embodiments the polyphenol component is an environmentally safer alternative for enhancing the efficacy of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one instead of some previously discovered fungicidal efficacy enhancement agents.

In noted embodiments the inventive combinations might comprise, additional component (3) pesticidal compound(s). In some embodiments the additional fungicidal component is a fungicide such as any of QiI fungicide, strobilurin fungicide, QoI fungicide, succinate dehydrogenase inhibitor (SDHI) fungicide; triazole (azole) fungicide (DMI), morpholine fungicide, etc. these fungicide and those above may have previously been included to enhance the efficacy of 5-fluoro- 4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one, though clearly enhancement with relatively environmentally safer polyphenol compounds is preferred.

In any event being able to enhance the efficacy of a fungicide such as 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one with a polyphenol compound having less of a deleterious effect on the environment than heretofore known synthetic pesticides as efficacy enhancing agents, must clearly be advantageous.

In some noted embodiments based on mixtures of the efficacy-enhancing group of fungicides together with fungicides exemplified by a compound represented by the following structure, , the inventive additional combination with the polyphenol-based compounds, can allow a reduction in the content of the efficacy-enhancing fungicide by 25% or more compared with the "fungicidally effective amount" of that fungicide, as defined herein without loss of activity.

In some noted embodiments based on mixtures of the efficacy-enhancing group of fungicides together with fungicides exemplified by a 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicidal compound represented by the following structure, , the inventive additional combination with the polyphenol-based compounds, can allow a reduction in the content of all of each of the efficacy-enhancing fungicide, and/or the 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides by between about 10-50% compared with the fungicidally effective amount of the combination of the same efficacy-enhancing fungicide together with the same 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides without loss of activity. Most commonly the reduction in fungicide content is between about 20% and about 40% without loss of fungicidal efficacy.

Typically, the level of fungicidal performance encountered with these inventive combinations of 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides with reduced content of efficacy-enhancing fungicides is actually improved when in combination with polyphenol-based compounds as compared to mixtures of the same 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides with the previously encountered unreduced content of the same efficacy-enhancing fungicides without polyphenol-based compound.

The present invention also provides as embodiments, increased effectiveness multi-component combinations comprising at least (1) an amount of polyphenol-based -component, and as component (2) an amount of at least one 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide compound represented by the following structure, ; and optionally, an additional component (3) fungicide which is different from the component (2) fungicide compound, wherein the combinations are more effective for treating a plant or soil against fungal and/or bacterial disease than if each component at the same amount is applied alone, and wherein if present, the amounts of compounds comprising component (3) or other fungicides are advantageously reduced compared to the amounts in previously encountered fungicidal combinations.

The present invention also provides as embodiments, a combination of at least two components: (1) an amount of polyphenol-based component, and as component (2) an amount of at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide, wherein the amount of polyphenol-based component (1) and the amount of the 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides comprising component (2), if applied together or in concert, etc., is more effective for treating plant or soil against fungal and/or bacterial infection than if each component at the same amount is applied alone without the other.

The present invention also provides as embodiments a combination comprising at least two components: (1) an amount of polyphenol-based component, and as component (2), an amount of a fungicide compound represented by the following structure, , wherein the amount of the fungicide compound is less than the fungicidally effective amount of that fungicide compound used alone rather than in the combination.

Thus, in many embodiments the polyphenol-based compound is an efficacy enhancer agent for 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides and considering the environmentally acceptable nature of many of these compounds, it would not be far-fetched to refer to them as environmentally safer fungicide efficacy enhancement agents.

In some embodiments, where the combination comprises a third component (3) comprising one or more efficacy/performance-enhancing fungicides, wherein the amount of efficacy-enhancing fungicide in the combination is less than when the fungicidally effective amount of that efficacy-enhancing fungicide is used with the same fungicide compound represented by the following structure, alone and not in combination with polyphenol-based component (1), or when the mixture of the fungicides of component (2) are used in absence of the polyphenol-based component (1).

In some embodiments the additional fungicides are efficacy-enhancing fungicides which have been added to enhance the efficacy of 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, although as discussed above, it is hoped that combinations of polyphenolic compounds may well obviate the need for them.

In some embodiments, minimal amounts of efficacy/performance-enhancing fungicide in component (3) are used in order to boost the fungicidally enhancing effects of the polyphenol-based compounds of component (1) on the fungicide compound represented by the following structure, of component (2).

. Without wishing to be bound by any theory, it may be that the function of the heretofore known efficacy-enhancing fungicides are changed when combined with the polyphenol-based compounds and they are not themselves antifungal to an appreciable degree in the combination, but rather as explained above, simply able to significantly enhance the activity of the polyphenol-based component in boosting the fungicidal activity of the component (2) fungicide, this may explain why such drastic reductions in efficacy-enhancing fungicide are made possible in the inventive combinations herein disclosed.

The present invention also provides as embodiments a combination comprising at least two components: component (1) an amount of polyphenol-based component, and as component (2), an amount of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone.

The Polyphenol-based component (1), is often, typically, or even advantageously comprised of a mixture of different chemical compounds each including at least two phenol functional groups.

In general, relatively environmentally "friendly’ or non-harmful polyphenol compounds will have an environmental advantage when enhancing the efficacy of fungicides such as 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides.

As many of the polyphenol compounds useful as component (1) in the inventive combinations are safer and/or lack deleterious effects they may be used in wide ranges of amounts and ratios with the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, such as 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one.

Thus, in the illustrative compositions and combinations the effective amounts of component (1) polyphenol compound in the list of ingredients vary greatly to allow for as wide a range of use as the researcher finds advantageous without wishing to limit the amount in the combination. This wide breadth of useable amounts of component (1) reflects the advantages that may be gained by using excess polyphenol compound even beyond what is required for simply enhancing the fungicidal efficacy of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one, which may include plant health benefits and other advantages discussed herein which are concomitant with their use.

However, typically concentrated compositions containing the inventive combinations, comprise between greater than zero and up to about 10% of the polyphenol-based compounds as component (1) based on the weight of the whole composition that also includes 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one as the component (2). Once these compositions are diluted prior to application the percentage content will clearly be reduced through dilution.

Thus, in some embodiments the invention is a composition comprising a multicomponent combination wherein component (1) comprises polyphenol-based compound and component (2) comprises 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one, wherein the polyphenol-based compound comprises between greater than 0 and 10% by weight of the entire composition.

In noted embodiments the polyphenol-based component comprises but is not limited to natural, naturally sourced or derived polyphenols. In some circumstances the naturally sourced polyphenol-based component (1) includes at least a portion of one or more synthetic polyphenol compounds without departing from the invention.

In some notedly advantageous embodiments, the polyphenol-based component comprises at least one polyphenol. In some circumstances the polyphenol-based component (1) of the combination of the invention, or compositions comprising the combination includes, or is in addition to at least a portion of one or more dispersants without departing from the invention.

Polyphenol-based compound of the invention is exemplified by a group including phenolic acids, stilbenes, lignans, hydrolyzable tannins, tannic acid, flavonoids and combination thereof.

Castalagin; extracts of water-soluble tannins; and extracts of water-soluble Proanthocyanidins.

In some embodiments, flavonoids refers but not limited to flavones, aurones, anthocyanins, leucoanthocyanidins, flavonols, flavanols, flavanones, chalcones, isoflavonoids, proanthocyanidins and combination thereof.

In some embodiments, the polyphenol-based component is comprised of one or more extracts which each comprise at least one structure/source of polyphenols.

In useful polyphenol component (1) embodiments, tannins are used which include various types of tannins, such as condensed and/or hydrolyzable tannins, and/or phlorotannins. Noted are, condensed tannins of the procyanidin and/or prodelphinidin type, such as of maritime pine (Pinus pinaster), of Chilean pine (Araucaria Araucana) , of Pecan nuts (pecan) , of Spruce (Picea abies), of Douglas, of fir etc,. and/or condensed tannins of the prorobinetinidin and/or profisetinidin type, such as of Mimosa (Acacia mearnsii, Acacia mollissima, Acacia mangium, Acacia catechu) , of Quebracho Schinopsis lorentzii, Schinopsis balansae) , of Gambier Uncaria gambir) , etc,. and/or hydrolysable tannins, such as of chestnut (Castanea sativa, Castanea vesca), of Tara Caesalpinia spinosa) , etc,. and/or -phlorotannins extracted from algae.

These tannins can be possibly employed also in their form purified by extraction with organic solvents, through processes such as acylation, methylation, ethoxylation, propoxylation, etc., and/or in their form modified or transformed by means of various chemical and physical reactions, such as polymerization, oxidation or enzymatic or chemical hydrolysis, and/or with the introduction of amino groups, so that the tannins can also be in the form of sulphited, sulphonated, oxidized, acetylated, esterified, ethoxylated or propoxylated substances, or possible mixtures thereof.

Noted are the polyphenol including, Flavonoids such as Anthocyanins, Chalcones, Dihydrochalcones, Dihydroflavonols, Flavanols, Flavanones, Flavones, Flavonols, and Isoflavonoids; Lignans; Alkylmethoxyphenols; Alkylphenols; Curcuminoids; Furanocoumarins; Hydroxybenzaldehydes; Hydroxybenzoketones; Hydroxycinnamaldehydes; Hydroxycoumarins; Hydroxyphenylpropenes; Methoxyphenols; Naphtoquinones; Phenolic terpenes; Tyrosols; Phenolic acids such as Hydroxybenzoic acids, Hydroxycinnamic acids, Hydroxyphenylacetic acids, Hydroxyphenylpentanoic acids and Hydroxyphenylpropanoic acids; and Stilbenes (phytoalexins).

Also noted are, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid 1700MW, and Resveratrol.

In some embodiments, the molecular weight of the polyphenol compounds of the present invention is between 100 and 2000 g/mol. In some embodiments, the molecular weight of the polyphenol compounds of the present invention is between 100 and 1700 g/mol. In some embodiments, the molecular weight of the polyphenol compounds of the present invention is between 100 and 15g/mol. In some embodiments, the molecular weight of the polyphenol compounds of the present invention is between 100 and 1200 g/mol. In some embodiments, the molecular weight of the polyphenol compounds of the present invention is between 100 and 1000 g/mol. In some embodiments, the molecular weight of the polyphenol compounds of the present invention is between 100 and 500 g/mol. The molecular weight may be any intermediate or range selected from any of the above indicated values.

Some compounds usefully included within the term polyphenol-based component (1) for combination with component (2) fungicides are listed below.

Clearly some of the polyphenol component (1) compounds listed will display a higher level of advantageous improvement than others when combined with a particular component (2) fungicidal compound selected from 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, for improving a particular crop, or for controlling and or preventing a particular fungal pathogen infection etc.

The following Component (1) polyphenol compounds are noted in combination with 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one, although as described this list cannot be seen as comprehensive or in any way limiting.

When two polyphenol compounds are equally useful as component (1), for enhancing the efficacy of 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides such as 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone, formulation considerations aside, it is perhaps worthwhile to select the more environmentally innocuous efficacy enhancing polyphenol. However often it is the most potent efficacy enhancing polyphenol compound used in order to obtain maximum beneficial plant effects with a smaller amount of the compound.

In some useful polyphenol component (1) embodiments, tannins are used which include various types of tannins, such as condensed and/or hydrolyzable tannins, and/or phlorotannins. Noted are, condensed tannins of the procyanidin and/or prodelphinidin type, such as of maritime pine (Pinus pinaster), of Chilean pine (Araucaria Araucana) , of Pecan nuts (pecan) , of Spruce (Picea abies), of Douglas, of fir etc,. and/or condensed tannins of the prorobinetinidin and/or profisetinidin type, such as of Mimosa (Acacia mearnsii, Acacia mollissima, Acacia mangium, Acacia catechu) , of Quebracho Schinopsis lorentzii, Schinopsis balansae), of Gambier Uncaria gambir), etc ,. and/or hydrolysable tannins, such as of chestnut (Castanea sativa, Castanea vesca), of Tara Caesalpinia spinosa), etc,. and/or -phlorotannins extracted from algae.

These tannins can be possibly employed also in their form purified by extraction with organic solvents, through processes such as acylation, methylation, ethoxylation, propoxylation, etc., and/or in their form modified or transformed by means of various chemical and physical reactions, such as polymerization, oxidation or enzymatic or chemical hydrolysis, and/or with the introduction of amino groups, so that the tannins can also be in the form of sulphited, sulphonated, oxidized, acetylated, esterified, ethoxylated or propoxylated substances, or possible mixtures thereof.

Noted are the polyphenol including, Flavonoids such as Anthocyanins, Chalcones, Dihydrochalcones, Dihydroflavonols, Flavanols, Flavanones, Flavones, Flavonols, and Isoflavonoids; Lignans; Alkylmethoxyphenols; Alkylphenols; Curcuminoids; Furanocoumarins; Hydroxybenzaldehydes; Hydroxybenzoketones; Hydroxycinnamaldehydes; Hydroxycoumarins; Hydroxyphenylpropenes; Methoxyphenols; Naphtoquinones; Phenolic terpenes; Tyrosols; Phenolic acids such as Hydroxybenzoic acids, Hydroxycinnamic acids, Hydroxyphenylacetic acids, Hydroxyphenylpentanoic acids and Hydroxyphenylpropanoic acids; and Stilbenes (phytoalexins).

Also noted are, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid 1700MW, and Resveratrol.

In some embodiments the polyphenol compounds of the polyphenol-based component (1) comprise Castalagin, either alone or with other natural polyphenol compounds In some noted and exemplified embodiments, polyphenol compounds of the polyphenol-based component (1) are extracts of water-soluble tannins and proanthocyanidins.

In some embodiments, the inventive combination further comprises at least one additional polyphenol-based component ingredient.

In some embodiments, wherein the fungicides of component (3) are included as additional fungicide they can be selected from any fungicidal compound that is found to be beneficially included with the component (2) fungicide.

In some embodiments the combinations of polyphenol compound, and 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone does not require any further fungicide. In some embodiments additional fungicides added to the inventive combinations can provide further advantages.

In some embodiments comprising three component combinations, a mixture of polyphenol-based component (1) and efficacy-enhancing fungicide of component (3) are provided as a single composition for combining with separately prepared or obtained composition(s) of component (2) comprising the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one of component (2), before application.

In several embodiments this combining is accomplished by mixing both types of composition in a Tank-mix, or else, the two compositions are applied separately in any of simultaneous, contemporaneous, concomitant, sequential and/or succession/successive applications.

In some embodiments comprising three component combinations comprising two different efficacy-enhancing fungicides as component (3), a mixture of polyphenol-based component (1) and one of the efficacy-enhancing fungicides of component (3) are provided as a single composition for combining with separately prepared or obtained composition(s) of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone of component (2) and the other of the efficacy-enhancing fungicides compounds of component (3), before application.

In several embodiments this combining is accomplished by mixing both types of composition in a Tank-mix, or else, the two compositions are applied separately in any of simultaneous, contemporaneous, concomitant, sequential and/or succession / successive applications.

As can be appreciated, mixtures of polyphenolic compounds with efficacy-enhancing fungicides can be considered an integral part of the invention and the embodiments of the instant invention where the amounts or concentrations of the efficacy-enhancing fungicides are significantly below the levels required to have a fungicidal effect. As can be immediately appreciated and/or understood, such a mixture of a Polyphenol compound together with sub-therapeutic negligibly fungicidal content of efficacy-enhancing fungicide compound, can be usefully considered as having only practical utility as a fungicidal combination when combined with e.g., 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone of component (2), rather than any simple fungicidal product of commerce as they are not significantly fungicidal alone given their sub-efficacious content. Thus, such a combination of Polyphenol-based (1) and a minimal content of efficacy-enhancing fungicide compound (3) can be termed a combination of Polyphenolic and efficacy-enhancing fungicide compounds, adapted for use in preparing the multi-component combinations of the invention where this combination behaves to enhance the effect of the polyphenol-based component. These mixtures of polyphenolic compounds with efficacy-enhancing fungicide compounds can usefully be provided in kit form together with a separate mixture of fungicidally active component (2) exemplified by 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone.

Without being bound by any theory, to the extent that the invention can be viewed in one aspect, as a method of enhancing the fungicidal effect of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone, by combining said fungicide compound with polyphenolic compounds, the minimal amounts of efficacy-enhancing fungicides used in the above embodiments can be viewed as boosting the fungicidal-enhancing power of the polyphenolic compounds, rather than displaying any significant pesticidal efficacy or even directly affecting the 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone itself.

Efforts to reduce the amounts of fungicides introduced into the environment are generally appreciated and thus if polyphenol compounds can allow for the effective fungicidal control by 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone without any other fungicides being needed as efficacy enhancers, an advantage to the environment is clear.

If the minimum fungicidally effective amount of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone for a particular pathogen is reduced, a clear advantage is achieved.

In some embodiments, the combination of the invention, comprises polyphenol-based component and a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide of formula I, , wherein R 1 is selected from H, C 1-C 6 alkyl, and C 1-C 6 alkoxy, and R 2 is selected from C 1-C 6 alkyl , phenyl, benzyl , and -CH 3-thiophenyl.

In some embodiments, the combination of the invention, comprises polyphenol-based component and 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone.

In some embodiments, the combination of the invention, comprises polyphenol-based component and the compound represented by the following structure, .

In some embodiments, the combination of the invention, comprises polyphenol-based component (1) and a compound with the CAS number 1616664-98-2 as component (2).

In some embodiments, the combination of the invention, comprises polyphenol-based component and flumetylsulforim.

In some embodiments, the combination of the invention, comprises polyphenol-based component, 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone and efficacy-enhancing fungicide.

In some embodiments, the combination of the invention, comprises polyphenol-based component, efficacy-enhancing pesticide, and 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone.

In some embodiments, the combination of the invention, comprises polyphenol-based component, efficacy-enhancing pesticidal compound, and 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide of formula I, , wherein R 1 is selected from H, C 1-C 6 alkyl, and C 1-C 6 alkoxy, and R 2 is selected from C 1-C 6 alkyl, phenyl, benzyl , and -CH 3-thiophenyl.

In some embodiments, the combination of the invention, comprises polyphenol-based component, additional pesticide, 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide of formula I, , wherein R 1 is selected from H, C 1-C 6 alkyl, and C 1-C 6 alkoxy, and R 2 is selected from C 1-C 6 alkyl, phenyl, benzyl, and -CH 3-thiophenyl, and a different additional pesticide.

In several forms of embodiments herein disclosed and/or alluded to, the polyphenol-based component includes combined extracts of natural water-soluble Tannins and Proanthocyanidins as sources of the polyphenols, and thus the polyphenol-based compounds herein inventively utilized in the inventive combinations, compositions and methods herein disclosed etc. are typically mixtures of several, often naturally sourced or derived, water-soluble Tannins and Proanthocyanidins, although as mentioned the invention is by no means limited to the use of extracts of natural water-soluble Tannins and Proanthocyanidins. Notably, the inclusion of synthetic polyphenol-based compounds has not yet been found to be any less useful or for that matter adversely affect the benefits that have been achieved with natural Tannins and Proanthocyanidins, and thus, the inclusion of synthetic polyphenol-based compounds in the inventive combinations either alone or in combination with natural polyphenol compounds is not a departure from the invention, and thus does not remove the combinations comprising them from the scope of protection being sought.

Proanthocyanidins are a class of polyphenols found in many plants. Chemically, they are oligomeric flavonoids. More complex polyphenols, having the same polymeric building block, form the group of Tannins.

Tannins are complex chemical substances derived from phenolic acids which are found in many species of plants. They are typically large polyphenolic molecules that bind readily with proteins, cellulose, starches, and minerals. In general, Tannins are found commonly in the bark of trees, wood, leaves, buds, stems, fruits, seeds, roots, and plant galls. Tannins are believed to help to protect the individual plant species. Tannins that become stored in the bark of trees, for example can, to some degree, protect the tree from being infected by certain bacteria or fungi.

Generally, the polyphenol-based compounds as component (1) can be used either in solid or liquid form.

For illustrative purposes, typical embodiments of the liquid forms of the polyphenol-based component include a liquid comprising any of 2.5%, 5%, 7.5%, 10%, 12.5%, 15%, 17.5%, 20%, 22.5%, 25%, 27.5%, 30%, 32.5%, 35%, 37.5%, 40%, 42.5% or 45%, of mixtures of several, often naturally sourced or derived water-soluble Tannins and Proanthocyanidins, or any of the other polyphenol compounds illustrated above. It may often be the type of formulation and the method of combination with the 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one which will be the deciding factor of which polyphenol compound is best. For example, qualities such as hydrophobicity or hydrophilicity or for that matter acidity or alkalinity may be more relevant to different formulation types. It is perhaps the breadth of such options that add to the advantages of using this type of efficacy enhancement agent.

In typical concentrated compositions the polyphenol-based compound comprises between greater than zero and about 10% by weight or volume of the entire composition comprising the combination of the polyphenol-based component (1) and the fungicidal component (2). Once these compositions are diluted prior to application the percentage content will be reduced through dilution.

Clearly, use of compositions comprising different numerical percentage content of polyphenol-based compounds as component (1) i.e. in dilute or concentrated forms, do not depart from the scope of this invention in any way but rather these above exemplified percentages make the calculations of ratios of components easier to compute.

In the embodiments herein listed, tabulated, and/or alluded to, the content of polyphenol-based component (1) is often, between about 10g/ha and about 350g/ha, and in several common instances the content of polyphenol-based component (1) is between about 40g/ha and about 90g/ha exemplified as, though not limed to, between 43.75g/ha and 87.5g/ha. Although safe polyphenol compounds may be used over and above their minimum requirements due to the lack of deleterious effects of an overage. In contrast, in some formulating embodiments the content of polyphenol-based component (1) is often measured or calculated as a weight percentage of the entire composition or combination. Typically, a formulator using this approach will add between greater than zero percent and about 10% of the polyphenol compound as component (1) by weight of the entire composition, these compositions are of the concentrated variety intended for dilution prior to fungicidal (pesticidal) application.

To be clear, when discussing the content of an agriculturally applied ingredient in an agricultural composition, particularly in concentrated form, it is often convenient to refer to the intended rate of application. For example, an ingredient content described as 10g/ha in a concentrate designed to be diluted before use, is understood to be an amount of that ingredient that when diluted and applied from a typical Tank-mix dilution and liquid spraying rates (e.g., 150 L/ha), will be applied 10g/ha. When the content of an ingredient in an agricultural composition is defined by g a.i./ha, it is clear that the concentrate has the same content even if the final dilution and/or spray rate is changed, this however is an accepted description of such ingredient content in agriculture.

As mentioned, the inclusion of further fungicides to the inventive combinations does not in any way depart from the scope of this invention, even if the additional fungicide is ultimately shown to be superfluous or even somewhat detrimental to the level of effect or improvement achieved by implementing the invention.

In some embodiments, the combination of the invention, comprises between about 10g/ha and 350g/ha of polyphenol-based component (1); and 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one fungicide as component (2), or between greater than zero and about ten percent of polyphenol-based component (1) by weight of the composition comprising the combination.

In some embodiments, the combination of the invention, comprises a composition containing the combination of the invention adapted for application of between about 10g/ha and 350g/ha of polyphenol-based component (1); and application of between about 1 g/ha to 500 g/ha of a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide as component (2).

In some noted embodiments, the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide compound is 5-fluoro-4-imino-3-methyl-1-[4-methyl(benzene-1-sulfonyl)]-3,4-dihydropyrimidin-2(1H)-one, CAS number 1616664-98-2, applied at an amount from 1 g/ha to 500 g/ha .

In some embodiments the polyphenol component (1) is utilized in the same manner as an agricultural adjuvant without being dependant on the amount or content of the active fungicidal component (2), and thus may be optimized in the same way as previously used adjuvants.

In some embodiments, where the component (2) fungicide compound is 5-fluoro-4-imino-3-methyl-1-[4-methyl(benzene-1-sulfonyl)]-3,4-dihydropyrimidin-2(1H)-one, the compound is applied at an amount from 1 g/Ha – 500 g/Ha. In some embodiments, the compound is applied at an amount from 5 g/ha to 120 g/ha. In some embodiments, the compound is applied at an amount from 1 g/ha to 100 g/ha. In some embodiments, the compound is applied at an amount from 1 g/ha to 75 g/ha. In some embodiments, the compound is applied at an amount from 1 g/ha to 50 g/ha. In some embodiments, the compound is applied at an amount from 1 g/ha to 25 g/ha. In some embodiments, the compound is applied at an amount from 1 g/ha to 15 g/ha. In some embodiments, the compound is applied at an amount from 2 g/ha to 13 g/ha. In some embodiments, the compound is applied at an amount from 5 g/ha to 10 g/ha. In some embodiments, the compound is applied at an amount from 15 g/ha to 100 g/ha.

In some embodiments, the component (2) fungicide compound is applied at an amount of about g/ha. In some embodiments, the compound is applied at an amount of about 6.25 g/ha. In some embodiments, the compound is applied at an amount of about 10 g/ha. In some embodiments, the compound is applied at an amount of about 12.5 g/ha. In some embodiments, the compound is applied at an amount of about 75 g/ha. In some embodiments, the compound is applied at an amount of about 100 g/ha. In some embodiments, the compound is applied at an amount of about 125 g/ha. In some embodiments, the compound is applied at an amount of about 150 g/ha. In some embodiments, the compound is applied at an amount of about 300 g/ha. In some embodiments, the compound is applied at an amount of about 500 g/ha.

As is well understood in this art of formulating pesticidal compositions, it is a common convention to refer to the content of an active ingredient in a pesticide composition in terms of the intended rate of application in grams active ingredient per hectare [g a.i./Ha], rather than the percentage content by weight or volume of the formulated composition. This is often the case given that compositions are often formulated as concentrates which are rarely applied as such but rather, they are intended for typical dilutions to final volume in typical spray tanks for application at typical volumes of spray per hectare. Such that the compositions of the inventive combinations for use in the spary rate embodiments above can be expressed as follows.

In some embodiments, the combination of the invention, comprises a composition containing between about 10g/ha and 350g/ha of polyphenol-based component (1); and between about 1 g/ha to 500 g/ha of a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicidefungicide as component (2).

In some embodiments, where the component (2) fungicide compound is 5-fluoro-4-imino-3-methyl-1-[4-methyl(benzene-1-sulfonyl)]-3,4-dihydropyrimidin-2(1H)-one, the composition comprises the compound at an amount from 5 g/ha to 120 g/ha. In some embodiments, the composition comprises the compound at an amount from 1 g/ha to 100 g/ha. In some embodiments, the composition comprises the compound at an amount from 1 g/ha to 75 g/ha. In some embodiments, the composition comprises the compound at an amount from 1 g/ha to g/ha. In some embodiments, the composition comprises the compound at an amount from 1 g/ha to 25 g/ha. In some embodiments, the composition comprises the compound at an amount from g/ha to 15 g/ha. In some embodiments, the composition comprises the compound at an amount from 2 g/ha to 13 g/ha. In some embodiments, the composition comprises the compound at an amount from 5 g/ha to 10 g/ha. In some embodiments, the composition comprises the compound at an amount from 15 g/ha to 100 g/ha.

In some embodiments, the composition comprises the compound at an amount of about 5 g/ha. In some embodiments, the composition comprises the compound at an amount of about 6.25 g/ha. In some embodiments, the composition comprises the compound at an amount of about 10 g/ha. In some embodiments, the composition comprises the compound at an amount of about 12.5 g/ha. In some embodiments, the composition comprises the compound at an amount of about 75 g/ha. In some embodiments, the composition comprises the compound at an amount of about 100 g/ha. In some embodiments, the composition comprises the compound at an amount of about about 1g/ha. In some embodiments, the composition comprises the compound at an amount of about 1g/ha. In some embodiments, the composition comprises the compound at an amount of about 3g/ha. In some embodiments, the compound is applied at an amount of about 500 g/ha.

Examples of the type of adaptation for controlling or establishing the intended rates of application of compositions containing the combinations, include providing the composition as a single composition of the two components in a fixed ratio as either a ready to spray composition including directions for the rate at which the composition should be applied for each hectare, or a kit containing concentrated compositions of each compomponent with directions of how much of each must be mixed and diluted in a Tank-mix together with directions of the rate at which the obtained Tank mix should be applied per hectare. Similarly, where there are fixed spraytank volumes and standard dilution rates, simply providing the appropriate ratio of components will ensure that the rates are applied and thus the fixed amounts of each component in the composition will be such an adaptation, as by simply diluting and spraying at standard spray rates will result in the appropriate spray rates. To the normally skilled practictioner of these arts other adaptations to control spray rates by establishing composition contents will be apparent and often known in the formulating arts.

Commonly encountered spray rates of the 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one in the compositions are between about 1g/ha and about 500g/ha such as, between 15 g a.i./Ha and 100 g a.i./Ha, and thus it useful in that example, to refer to the content of the compositions as being adapted so as to contain 15 g a.i./Ha and 100 g a.i./Ha5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one.

As a non-limiting example, employing the inventive combinations of polyphenol compound(s) and 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, a spray rate of between about 0.2 ppm and about 8.4 ppm, such as 0.18ppm, 1.18ppm, 2.56ppm, 2.27ppm, 8.41ppm etc., of tank-mix or ready mix 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one is sufficient to achieve enhanced performance, control and or protection (curative or protectant), as compared with the same amount sprayed in the abscence of the polyphenol compound.

In some embodiments, the combination of the invention, comprises a composition containing the combination of the invention adapted for application of between about 10g/ha and 350g/ha of polyphenol-based component (1); and application of between about 1g/ha and about 500g/ha of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one as component (2), although rates within a more narrower range are more typical.

In some embodiments, the combination of the invention, comprises a composition containing the combination of the invention adapted for application of between about 10g/ha and 350g/ha of polyphenol-based component (1); and application of between about 1g/ha and about 500g/ha of a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide as component (2) and a different additional pesticide fungicide as component (3).

Wherein component (2) is exemplified typically by 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one and non-limiting application rates include, 1 g/ha to 500 g/ha of component (2), such as some illustrative rate ranges displayed below.

Non-limiting examples of spray rates of component (2) include being selected from the group of, from 5 g/ha to 120 g/ha; from 1 g/ha to 100 g/ha; from 1 g/ha to 75 g/ha; from 1 g/ha to 50 g/ha; from 1 g/ha to 25 g/ha: from 1 g/ha to 15 g/ha: from 2 g/ha to 13 g/ha; from 5 g/ha to 10 g/ha;from 15 g/ha to 100 g/ha; about 5 g/ha; about 6.25 g/ha; about 10 g/ha; about 12.5 g/ha;about 15 g a.i./ha; about 75 g/ha; about 100 g/ha; about 125 g/ha; about 150 g/ha; about 300 g/ha; and about 500 g/ha.

In some embodiments , a composition containing the inventive combination comprises 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one as the compound of component (2) in an amount ranging from about 0.1 % to 90 % by weight based on the total weight of the composition, sometimes from about 0.1% to 20% by weight based on the total weight of the composition .

In some embodiments , the amount of the compound 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one as component (2) in the composition is from about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5% to about 90%, 93%, 95%, 98%, or 99% by weight based on the total weight of the composition. The formulation types of the compositions comprising the inventive compositions will be often dependent on the use environment and the physical and chemical characteristics of the ingredients and other typical formulation considerations, some will be more optimum than others in individual situations. Obviously, a concentrated formulation will have a far higher active ingredient content than a ready to spray or diluted tank mix, which may contain added adjuvants.

In some embodiments, the amount of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one in the composition is from about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5% to about 90%, 93%, 95%, 98%, or 99% by weight based on the total weight of the composition .

In some embodiments, the amount of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one in the composition is about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% by weight based on the total weight of the composition .

In some embodiments, the amount of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one in the composition is about 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% by weight based on the total weight of the composition.

While the polyphenol-based component (1) is often safe over a very wide range of concentrations without departing from the invention, it is often practically convenient to employ particular concentrations for formulation considerations although in dilute environments the component (2) might act akin to an adjuvant far exceeding the amount that might be included in a concentrate simply from solubility and stability point of view.

In some embodiments, the combination of the invention, comprises between about 10g/ha and 350g/ha, typically about 40g/ha and about 90g/ha such as, between about 43.75g/ha and 87.5g/ha of polyphenol-based component (1) such as about 52 g/Ha; and between about 1g/ha and about 500g/ha of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one as component (2), combined with, additional fungicides,wherein, non-limiting examples of component (2) content in the combinations are, from 5 g/ha to 120 g/ha; from 1 g/ha to 100 g/ha; from 15 g/ha to 100 g/ha; from 1 g/ha to 75 g/ha; from 1 g/ha to 50 g/ha; from 1 g/ha to 25 g/ha: from 1 g/ha to 15 g/ha: from 2 g/ha to 13 g/ha; from 5 g/ha to 10 g/ha; from 15 g/ha to 100 g/ha; about 5 g/ha; about 6.25 g/ha; about 10 g/ha; about 12.5 g/ha; about g a.i./ha; about 75 g/ha; about 100 g/ha; about 125 g/ha; about 150 g/ha; about 300 g/ha; and about 500 g/ha.

In some embodiments, the combination of the invention, comprises between about 10g/ha and 350g/ha typically about 40g/ha-90g/ha (e.g., 43.8 – 87.5 g/ha) of polyphenol-based component (1); and between about 1g/ha and about 500g/ha of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, as component (2) combined with different additional pesticide(s) such as fungicide, selected from about 200g/ha-500g/ha, typically about 300g/ha or about 400g/ha-1200g/ha commonly about 700g/ha; about 400g/ha-1500g/ha commonly about 700g/ha; as component (3), wherein each range relates to the commonly encountered rates of application for different optional different additional pesticide(s).

In some embodiments, the combination of the invention, comprises between about 10g/ha and 350g/ha of polyphenol-based component (1); between about 1g/ha and about 500g/ha of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one as component (2) and a different additional pesticidal compoundas component (3), wherein, non-limiting examples of component (2) content in the combinations are, from 5 g/ha to 120 g/ha; from 1 g/ha to 100 g/ha; from 15 g/ha to 100 g/ha; from 1 g/ha to 75 g/ha; from 1 g/ha to 50 g/ha; from 1 g/ha to 25 g/ha: from 1 g/ha to 15 g/ha:from 2 g/ha to 13 g/ha; from g/ha to 10 g/ha; from 15 g/ha to 100 g/ha;about 5 g/ha; about 6.25 g/ha; about 10 g/ha; about 12.5 g/ha;about 15 g a.i./ha; about 75 g/ha; about 100 g/ha; about 125 g/ha; about 150 g/ha; about 300 g/ha; and about 500 g/ha.

In some embodiments, the combination of the invention, comprises between about 10g/ha and 350g/ha of polyphenol-based component (1); between about 1g/ha and about 500g/ha of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one as component (2) and additional fungicidal compound(s), as component (3). wherein, non-limiting examples of component (2) content in the combinations are, from 5 g/ha to 120 g/ha; from 1 g/ha to 100 g/ha; from 15 g/ha to 100 g/ha; from 1 g/ha to 75 g/ha; from 1 g/ha to 50 g/ha; from 1 g/ha to 25 g/ha: from 1 g/ha to 15 g/ha: from 2 g/ha to 13 g/ha; from 5 g/ha to 10 g/ha; from 15 g/ha to 100 g/ha; about 5 g/ha; about 6.25 g/ha; about 10 g/ha; about 12.5 g/ha; about 15 g a.i./ha; about 75 g/ha; about 100 g/ha; about 125 g/ha; about 150 g/ha; about 300 g/ha; and about 500 g/ha.

In some embodiments, the combination of the invention, comprises between about 10g/ha and 350g/ha, typically about 40g/ha and about 90g/ha such as, between about 43.75g/ha and 87.5g/ha of polyphenol-based component (1); and between about 1g/ha and about 500g/ha of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one as component (2), often combined with one or more different additional pesticidal compound(s)as component (3), wherein, non-limiting examples of component (2) content in the combinations are, from 1 g/ha to 500 g/ha; from 5 g/ha to 120 g/ha; from 1 g/ha to 100 g/ha; from 15 g/ha to 1g/ha; from 1 g/ha to 75 g/ha; from 1 g/ha to 50 g/ha; from 1 g/ha to 25 g/ha: from 1 g/ha to 15 g/ha: from 2 g/ha to 13 g/ha; from 5 g/ha to 10 g/ha; from 15 g/ha to 100 g/ha;about 5 g/ha; about 6.25 g/ha; about 10 g/ha; about 12.5 g/ha;about 15 g a.i./ha; about 75 g/ha; about 100 g/ha; about 125 g/ha;about 150 g/ha; about 300 g/ha; and about 500 g/ha.

In noted embodiments comprising polyphenol-based component (1), 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one as component (2), component (3) does not comprise any additional fungicide but rather, comprises only one or more different additional non-fungicidal pesticide compound(s) as component (3) .

Of course, in many circumstances the inventive combinations are useful in compositions without any further pesticidally active ingredients at all, other than the combination of component (1) polyphenol-based compounds and 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one as component (2), together with additives suitable for agricultural application.

In several embodiments, the combinations of the invention (and compositions comprising them), comprise about 40g/ha - 90g/ha commonly, about 43.75g/ha - 87.5g/ha, combined extracts of natural water-soluble Tannins and Proanthocyanidins as polyphenol-based component (1), between about 1g/ha and about 500g/ha of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one as component (2). Although in some embodiments other polyphenol compounds are specifically included within the scope of this invention as component (1) which are not necessarily combined extracts of natural water-soluble Tannins and Proanthocyanidins as detailed in this disclosure and thus may replace them the any of the embodiments if they display the same or comparable advantages.

In several embodiments, the combination of the invention, comprises about 40g/ha - 90g/ha commonly, about 43.75g/ha-87.5g/ha, combined extracts of natural water-soluble Tannins and Proanthocyanidins as polyphenol-based component (1), between about 1g/ha and about 500g/ha of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one as component (2) and for example, 8.75g/ha of a different pesticidal efficacy enhancement agent as component (3). The illustrative example of 8.75g/ha of a different pesticidal efficacy enhancement agent above, is illustrative of a sub-effective content of the pesticidal efficacy enhancement agent where a pesticidal amount as a solo treatment would require an order of magnitude more (e.g., at least times greater), to be fungicidally efficacious alone.

As mentioned, in some embodiments other polyphenol compounds are specifically included within the scope of this invention as component (1) which are not necessarily combined extracts of natural water-soluble Tannins and Proanthocyanidins as detailed in this disclosure and thus may replace them the any of the embodiments if they display the same or comparable advantages. wherein, in the above embodiments non-limiting examples of component (2) content in the combinations are from 1 g/Ha – 500 g/Ha selected from the group including, from 5 g/ha to 120 g/ha; from 1 g/ha to 100 g/ha; from 15 g/ha to 100 g/ha;from 1 g/ha to 75 g/ha; from 1 g/ha to 50 g/ha; from 1 g/ha to 25 g/ha; from 1 g/ha to 15 g/ha:from 2 g/ha to 13 g/ha; from 5 g/ha to 10 g/ha; from 15 g/ha to 100 g/ha; about 5 g/ha; about 6.25 g/ha; about 10 g/ha; about 12.5 g/ha; about 15 g a.i./ha; about 75 g/ha; about 100 g/ha; about 125 g/ha; about 150 g/ha; about 300 g/ha; and about 500 g/ha.

In some embodiments, the combination of the invention, comprises a combination of components (1) and (3) for combination with the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides of component (2) selected from any one of the following mixtures or other mixtures that maintain the ratios of each of the following, Polyphenol = 88 + different additional pesticidal compound(A) g/ha, about 12: Polyphenol = 88 + 1st different additional pesticidal compound (A) 7.5 g/ha + 2nd different additional pesticidal compound (B) 600g/ha, about 12:1: Polyphenol = 44 + 1st different additional pesticidal compound (A) 7.5 g/ha, about 6: Polyphenol = 44 + 1st different additional pesticidal compound (A) 7.5 g/ha, + 2nd different additional pesticidal compound (B)600g/ha, about 6:1: Polyphenol = 87.5 + 1st different additional pesticidal compound (A) 175g/ha, about 1: Polyphenol = 87.5 + 1st different additional pesticidal compound (A) 175g/ha, + 2nd different additional pesticidal compound (B)600g/ha, about 1:2:3.4 [~ 1:2:3] Polyphenol = 44 + 1st different additional pesticidal compound (A) 8.75g/ha, about 5: Polyphenol = 44 + 1st different additional pesticidal compound (A) 8.75g/ha + 2nd different additional pesticidal compound (B)600g/ha, about 5:1: Polyphenol = 87.5 + 1st different additional pesticidal compound (A) 8.75g/ha, about 10: Polyphenol = 87.5 + 1st different additional pesticidal compound (A) 8.75g/ha + 2nd different additional pesticidal compound (B)600g/ha, about 10:1: Polyphenol = 44 + 1st different additional pesticidal compound (A) 3.75 g/ha about 12: Polyphenol = 22 + 1st different additional pesticidal compound (A) 3.75 g/ha + 2nd different additional pesticidal compound (B)300g/ha about 6:1: Polyphenol = 7.5g/ha + 1st different additional pesticidal compound (A) 10g/ha, about 3:4 Polyphenol = 7.5g/ha + 1st different additional pesticidal compound (A) 10g/ha, + 2nd different additional pesticidal compound (B)300g/ha about 3:4:1 Polyphenol = 15g/ha + 1st different additional pesticidal compound (A) 20g/ha about, 3:4.

Polyphenol = 15g/ha + 1st different additional pesticidal compound (A) 20g/ha + 2nd different additional pesticidal compound (B)300g/ha about, 3:4:120.

Polyphenols + 1st different additional pesticidal compound (A) 30% Polyphenols + 1st different additional pesticidal compound (A) 3% In the above illustrations it is clear that generally the type of 2nd different additional pesticidal compound (B) has a useful content much larger than 1st different additional pesticidal compound (A).

In some particularly noted embodiments, the component (2) 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides for combining with the above combination of components (1) and (3), are chosen from one or more compounds of formula I, , wherein R 1 is selected from H, C 1-C 6 alkyl, and C 1-C 6 alkoxy, and R 2 is selected from C 1-C 6 alkyl, phenyl, benzyl, and -CH 3-thiophenyl.

In particular embodiments the combination of the invention is prepared by combining a composition of Polyphenol-based compound with a 1st additional pesticidal compound (not component (2)) [components (1) and (3)] with a separate composition of one or more 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, and optionally a 2nd different additional pesticidal compound (B) [component (2) or component (2) + component (3)]. The preparative combining can be at the point of use or Tank-mix from a kit or from separate commercially available compositions etc., comprising the two compositions, or from compositions with instructions or otherwise adapted to be combined within the scope of this invention.

In some embodiments, the combination is mixture. In some embodiments the combination is a kit of parts intended or adapted for mixing before application. In some embodiments the parts of the kit are individual compositions that are both diluted combined and/or mixed.

In some embodiments, the weight ratio of the polyphenol-based component (1) to component (2) comprising 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) in any combination disclosed or alluded to herein is from about 1:100 to about 100:1 In some embodiments, the weight ratio of the polyphenol-based component (1) to component (2) comprising 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) in any combination disclosed or alluded to herein is from about 1:25 to about 25:1. In some embodiments, the weight ratio of the polyphenol-based component (1) to component (2) comprising 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) in any combination disclosed or alluded to herein is from about 1:10 to 10:1. In some embodiments, the weight ratio of the polyphenol-based component (1) to component (2) comprising 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) in any combination disclosed or alluded to herein is from about 1:5 to 5:1. In some embodiments, the weight ratio of the polyphenol-based component (1) to component (2) comprising 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) in any combination disclosed or alluded to herein is from about 1:2 to 2:1 In some embodiments, the weight ratio of the polyphenol-based component (1) to component (2) comprising 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) in any combination disclosed or alluded to herein is from about 1:1.

In some embodiments the component (2) 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide is a combination of two or more fungicides from the same fungicidal classification (mode of action), group or from different fungicidal classification groups, fungicides being classified either by chemical structure or their mode of action.

In some embodiments, a difference in fungicidal group refers to, but is not limited to the differences in the chemical structure(s) and/or mode of action of the fungicides.

In this disclosure, any mention of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, should be considered to be applicable to other 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicidal molecules unless otherwise specifically excluded or the context makes clear otherwise.

In some embodiments the combination is pesticidally efficacious though due to the choice of component (1) the efficacy is most prominent in addressing pests other than fungi such as microbial, arthropodal, mollusk or viral pests and the like, the principle remains the same as regards advantages of combination of polyphenol-based compounds as component (1) and N3-substituted-N1-sulphonyl-5-fluoropyrimidine compounds and/or derivatives as component (2).

In some embodiments the invention is a multi-component combination of one or more polyphenol-based compounds as component (1) and one or more pesticidal N3-substituted-N1-sulphonyl-5-fluoropyrimidine compounds and/or derivatives as component (2). In some embodiments the polyphenol compound(s) are natural or naturally sourced compounds which have no significant deleterious environmental impact across a wide range of amounts. In some embodiments the polyphenol is water soluble. As mentioned throughout this disclosure in many embodiments the polyphenol component (1) may be or may include any of naturally sourced or derived polyphenol-based compounds, and/or one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; and/or one or more of, extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1- enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol.

In some embodiments, the inventive combination of polyphenol compound(s) and 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one comprises an improved combination in that it reduces the level of environmentally injurious impact if any, or the known detrimental environmental impacts of one or more of the additional fungicides that are included in the combination for example as efficacy enhancement agents, as compared to when they are each employed independently without the polyphenol compound.

In some embodiments, the inventive combination comprises an improved combination in that it is synergistic, inter alia, in its fungicidal efficacy, or other beneficial attribute associated with any one or more of the active compounds that are included in the combination as compared to when they are each employed independently.

In some embodiments, the combination comprises improved combinations in that they are synergistic, inter alia, in their fungicidal efficacy, or other beneficial attribute associated with the combination of active compounds of component (2) and component (3), when present, that are included in the combination together with component (1) as compared to when only component (2) and additional pesticide component (3) when present, is employed in the absence of component (1). In many embodiments it is the improvement in the agricultural activity of the component (2) that is most significant, and not any reduction in the amount applied that simply maintains the typical application rates with improved efficacy.

In some embodiments, the combination comprises an improved combination in that the amount of the polyphenol-based component (1) and the amount of component (2) comprising at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide are more effective in combination application as described previously, for treating a plant or locus against fungal and/or bacterial infection than when the amount of the polyphenol-based component (1) and the amount of component (2) 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide are applied alone without the other.

In some embodiments, the combination of the invention comprises an improved combination in that the amount of the polyphenol-based component (1), and the amount of component (2) comprising at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide are more effective for treating a plant or locus against fungal and/or bacterial/microbial infection if applied in combination than if the same amount of the component (2) is not applied in combination with the same amount of the polyphenol-based component.

In some embodiments, the combination comprises an improved combination in that the amount of the polyphenol-based component (1) is more effective for treating a plant or locus against fungal infection if applied in combination with the amount of the component (2) comprising 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide than if the same amount of the polyphenol-based component is not applied in combination with the same amount of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide In some embodiments, the combination comprises an improved combination in that the amount of the polyphenol-based component (1) improves the fungicidal efficacy of the amount of the component (2) fungicide(s) compared to when the same amount of the fungicide(s) is applied not in combination with the amount of the polyphenol-based component. In some embodiments, the locus is soil. In many embodiments discussed the preferred 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide is the compound, 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one represented by the following structure, .

In some embodiments, the combination comprises an improved combination in that the amount of the polyphenol-based component (1) improves the beneficial effects of applying the amount of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) component (2) compared to when the same amount of the fungicide(s) is not applied in combination with the amount of the polyphenol-based component. These beneficial effects are any of improved emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance or improved non biotic stress mitigation (e.g. against drought, heat, salt, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), reduced phytotoxicity, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), shortening of stalks, increased diameter of stalks, increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination.

In some embodiments, the invention comprises an adapted composition of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) wherein the adaptation is to provide beneficial effects when brought into contact with plants which benefits are any, some or all of, improved emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance or improved non biotic stress mitigation (e.g. against drought, heat, salt, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), reduced phytotoxicity, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), shortening of stalks, increased diameter of stalks, increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination.

The adaptation of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide comprises combining one or more polyphenol compounds with the fungicide.

The adaptation can clearly include packaging the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide in a together with instructions for adding or including a polyphenol compound with the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide when preparing a ready-mix or tank-mix composition for application in a crop or crop plant environment, or soil.

Envisioned adapted compositions are adapted compositions which comprise both 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one as well as one or more additional pesticidal/fungicidal ingredients.

In some embodiments, the combination of the invention comprises an improved three-component combination in that the amount of one or more additional pesticidal ingredients of component (3) are significantly reduced (or can be), without any loss of efficacy when applied in combination with the amount of the polyphenol-based component (1) and the amount of component (2) comprising at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide in combination application as described previously, for treating a plant or locus against fungal and/or bacterial infection, compared to combinations that include the same amount of component (2) 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) and the same one or more additional pesticidal/fungicidal ingredients of component (3) applied without the amount of the polyphenol-based component (1).

In some multi-component combination embodiments, fungicidal efficacy of the compounds comprising component (2), is increased by at least 10%, about 20% or more, or about 30% and above, compared to when the same amount of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide component (2) compound(s) is/are applied alone. In some embodiments, fungicidal efficacy is increased by at least 50%, about 100% or more, about 200% or more or about 300% or more, compared to when the same amount of the fungicide is applied alone. Thus enabling reduction of the amount of 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one required for a particular level of fungicidal effect and thus lowering the environmental impact (if any), of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide which is commonly related to the actual amount of the compound introduced into the environment rather than necessarily to its fungicidal efficacy.

In some embodiments, fungicidal efficacy is measured in a treated area of the plant. In some embodiments, fungicidal efficacy is measured in an untreated area of the plant. In some embodiments, fungicidal efficacy is increased in a treated area of the soil or locus. In some embodiments, fungicidal efficacy is increased in an untreated area of the soil or locus.

In some embodiments, fungicidal efficacy is measured at least 7 days after initial and/or each, treatment, or application. In some embodiments, fungicidal efficacy is measured at least 14 days after initial and/or each, treatment, or application. In some embodiments, fungicidal efficacy is measured at least 21 days after initial and/or each, treatment, or application. In some embodiments, fungicidal efficacy is measured at least 28 days after initial and/or each, treatment, or application.

In some embodiments, the combination comprises an improved combination in that a substantially similar level of fungicidal efficacy is achieved by using a lesser amount of the polyphenol-based component and/or the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4- dihydropyrimidin-2(lH)-one pesticide. This reduces the level of environmental impact heretofore associated with an equivalent level of fungicidal efficacy.

In some embodiments, the amount of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one of component (2) the inventive compositions is/are less than the fungicidally effective amount of the fungicide when the fungicide is used alone.

In some embodiments, the combination comprises an improved combination in that the amount of the polyphenol-based component is effective to increase sensitivity of the fungus to the amount of the 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one component (2), compared to the sensitivity of the fungus to the amount of the fungicide when it is not applied in combination with the amount of the polyphenol-based component.

In some embodiments, the combination comprises an improved combination in that the amount of the polyphenol-based component is effective to increase bioavailability of the amount of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one compared to the bioavailability of the amount of the additional fungicide when it is not applied in combination with the amount of the polyphenol-based component.

In some embodiments, the combination comprises an improved combination in that the amount of the polyphenol-based component is in the range which is effective to increase bioavailability of the amount of the 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one component (2) compared to the bioavailability of the amount of the additional fungicide when it is not applied in combination with the amount of the polyphenol-based component.

In some embodiments, the inventive combination comprises an improved combination in that the inclusion of one or more polyphenol compounds effectively increases the bioavailability of the amount of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one component (2) fungicide compared to the bioavailability of the amount of the component (2) fungicide when it is not applied in combination with the amount of the polyphenol-based component.

While not wishing to be bound by theory, it may be that the increases in bioavailability of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s) alluded to above, which are typically achieved by the combination of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one with Polyphenol-based compound, allows for application of combinations comprising reduced amounts of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one fungicides without any loss in fungicidal efficacy. Clearly there are environmental advantages to any reduction of any biologically active chemical compounds released into the soil and or water.

In some embodiments, the combination comprises an improved combination in that it is more effective in treating the plant or locus against fungal and/or bacterial/microbial infection than when each fungicide comprising component (2) at the same amount is applied alone.

In some embodiments, wherein fungicide component (2) of the inventive multi-component combination comprises two or more individual compounds chosen from 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, the combination of these fungicides is foreseeably even more effective in treating the plant or locus against fungal infection than if the same fungicidal compounds were applied in combination at the same amount in the absence of polyphenol-based component (1).

In some embodiments, the combination comprises an improved combination in that the amount of the fungicide compounds of component (2) and the amount of the polyphenol-based component (1) are more effective in combination for treating a plant or locus against fungal and/or bacterial/microbial infection than when the amount of the polyphenol-based component and the amount of 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide are applied alone. In some embodiments, the combination of the polyphenol-based component (1) and at least one of the component (2) fungicides is more effective in treating the plant or soil against fungal infection than when the fungicide compound(s) component is applied alone at the same amount or rate.

In some embodiments, the combination of the invention comprises one or more of, combination, mixture and/or compositions and the combination of the polyphenol-based component (1) and at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide compounds, exemplified by 5-fluoro-4-imino-3-methyl-1-tosyl-3,dihydropyrimidin-2(1H)-one, is more effective in treating a plant or soil against fungal infection than when each fungicide compound at the same amount is applied alone, and not in combination-application with the inventive polyphenol-based compounds.

In some embodiments, treating a plant or locus against fungal infection comprises inhibiting fungal mycelium formation.

In some embodiments, treating a plant or locus against fungal and/or bacterial infection comprises combating phytopathogenic diseases on the plant or locus.

In some embodiments, treating the plant or locus against fungal and/or bacterial infection comprises protecting the plant or locus from fungal and/or bacterial attack.

In some embodiments, treating the plant or locus against fungal infection comprises preventing fungal and/or bacterial infection of the plant or locus.

In some embodiments, treating the plant or locus against fungal and/or bacterial infection comprises controlling fungal and/or bacterial disease affecting the plant or locus.

In some embodiments, treating the plant or locus against fungal and/or bacterial infection comprises controlling a fungal and/or bacterial pathogen, a fungal and/or bacterial pathogen group or a fungal and/or bacterial pathogen class affecting the plant or locus.

In some embodiments, treating the plant or locus against fungal and/or bacterial infection comprises controlling a fungal disease caused by a fungal and/or bacterial pathogen, a fungal and/or bacterial pathogen group or a fungal and/or bacterial pathogen class affecting the plant or locus.

In some embodiments, treating the plant or locus against fungal and/or bacterial infection comprises reducing fungal and/or bacterial infection of the plant or locus.

In some embodiments, the combination comprises an improved combination in that it prolongs the period of protection against fungal and/or bacterial infection and/or control of fungal and/or bacterial infection than when the amount of the polyphenol-based component and the amount of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one fungicide are applied alone.

In some embodiments, the period of protection against fungal infection and/or control of fungal and/or bacterial infection is prolonged by at least 7 days, 14 day, 21 days, or 28 days.

In some embodiments, the combination comprises an improved combination in that it reduces the amount of time needed to achieve a level of fungal and/or bacterial control than when the amount of the polyphenol-based component and the amount of 5-fluoro-4-imino-3-methyl-1-tosyl-3,dihydropyrimidin-2(1H)-one fungicide are applied alone.

A non-limiting example for reduction of the amount of time needed to achieve a level of fungal and/or bacterial control is, if each 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide is applied alone achieves 50% control of fungal disease days after application, the combination disclosed herein with polyphenol compound achieves 50% control of fungal and/or bacterial diseases 2 days after application where each combination, mixture and/or compositions is applied at the same or equivalent amount.

In some embodiments, the amount of time needed to achieve a level of fungal and/or bacterial control is reduced by at least 1 day, 2 days, 3 days, 4 day, 5 days, 7 days, 10 days, 14 days or days, or 28 days.

Although as should be abundantly clear, any reduction in the time required to achieve control or treatment etc. is advantageous and a composition that is able to achieve even minor reduction is within the scope of invention although generally the greater the reduction in time, the better.

In some embodiments, the combination comprises an improved combination in that it improves plant development compared to the development of a plant affected by the same type and degree of fungal and/or bacterial infection to which the combination is not applied. In some embodiments, the plant is a crop plant. In some embodiments, the additional fungicide as part of the combination comprises more effective in improving plant development than if applied at the same amount alone. In some embodiments, the polyphenol-based component as part of the combination is more effective in improving plant development than if applied at the same amount alone.

In some embodiments, the plant development is improved by treating the plant against fungal and/or bacterial attack.

In some embodiments, improving plant development comprises enhancing crop plants. In some embodiment, improving plant development comprises improving plant quality.

Improving plant development includes, but is not limited to, enhancing the root systems, enhancing shoot of the plant, enhancing plant vigor, enhancing greening effect on leaves and/or enhancing plant potential yield.

In some embodiments, improving plant development comprises enhancing the root system. In some embodiments, enhancement in root system is measured by root weight. In some embodiments, root weight is increased by at least 1%, 5%, 10, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.

In some embodiments, the combination is more effective in controlling pathogen than each of the fungicidal active ingredients in a combination used alone or as combination of one alone.

In some embodiments, the combinations display synergistic effect between polyphenol-based component and the at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide.

In some embodiments, the combinations display synergistic effect between polyphenol-based component and the at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide.

In some embodiments, the amount of polyphenol-based component and the amount of the at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides if applied in combination is more effective in treating a plant or soil against fungal and/or bacterial infection than if each fungicide at the same amount is applied alone.

In some embodiments, the amount of polyphenol-based component and the amount of the at least one additional fungicide if applied together is more effective in treating a plant or soil against fungal infection than if each fungicide at the same amount is applied alone.

In some embodiments, the amount of polyphenol-based component, the amount of the at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides in the combination, mixture and/or composition if applied in combination, is more effective in treating a plant or soil against fungal infection than if each fungicide at the same amount is applied alone.

In noted embodiments, the combinations according to the invention may also comprise more than one of the active components (a), (b), (c), (d) (e) below, increasing and/or broadening of the spectrum of disease control when desired. (a) a QiI fungicide, (b) a strobilurin fungicide, (c) a succinate dehydrogenase inhibitor (SDHI) fungicide, (d) a triazole fungicide and (e) a morpholine fungicide.

Embodiments of the present invention include providing methods of treating a plant or locus against fungal and/or bacterial infection comprising applying a combination of (1) an amount of a polyphenol-based component as previously described, and (2) at least one 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide(s), exemplified by 5-fluoro-4-imino-3-methyl-1-[4-methyl(benzene-1-sulfonyl)]-3,4-dihydropyrimidin-2(1H)-one, to the plant or locus so as to thereby treat the plant or locus against fungal and/or bacterial infection, wherein (i) the method is more effective against fungal and/or bacterial infection than when the amount of the polyphenol-based component and the amount of the fungicide(s) are applied alone, and/or (ii) the amount of the polyphenol-based component improves the fungicidal efficacy of the amount of the fungicide(s) compared to when the same amount of the fungicides are not applied in combination with the amount of the polyphenol-based component.

An embodiment of the present invention provides a combination for controlling disease caused by pathogen in plant, comprising (1) an amount of polyphenol-based component and as component (2), 1 g/Ha – 500 g/Ha of at least one fungicide selected from the group of 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides. The most notable of these fungicides is 5-fluoro-4-imino-3-methyl-1-[4-methyl(benzene-1-sulfonyl)]-3,4-dihydropyrimidin-2(1H)-one due to the amount of experience in studies.

An embodiment of present invention provides a method for controlling disease caused by pathogen in plant, comprising applying a combination of (1) an amount of polyphenol-based component and as component (2), 1 g/Ha – 500 g/Ha of at least one fungicides selected from the group of 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin- 2(lH)-one fungicides, to the plant, propagation material of the plant, and/or a locus of the plant. The most notable of these fungicides is 5-fluoro-4-imino-3-methyl-1-[4-methyl(benzene-1-sulfonyl)]-3,4-dihydropyrimidin-2(1H)-one due to the amount of experience in studies.

In some embodiments, the method comprises applying polyphenol-based component and the fungicide at any one of the rates described herein.

In some embodiments, the amount of the component (2) compound exemplified by flumetylsulforim in the inventive composition is about 0.1 % , 0.5 % ,1 % , 1.5 % , 2 % , 2.5 % , % , 3.5 % , 4 % , 4.5 % , 5 % , 10 % , 15 % ,20 % , 25 % , 30 % , 35 % , 40 % , 45 % , 50 % , % , 60 % , 65 % ,70 % , 75 % , 80 % , 85 % , 90 % or 95 % by weight based on the total weight of the composition. All numbers as throughout prefaced by "about" specifically including ±10% of the value stated.

The rate at which the combination, mixture, or composition according to embodiments of the invention is applied will depend upon the particular type of fungus and/or bacteria to be controlled, the degree of control required and the timing and method of application.

In some embodiments, the combination, mixture, or composition is applied at a rate from about grams of total active ingredient per hectare (g a.i./ha) to about 2000g a.i./ha based on the total amount of active ingredients in the combination, mixture, or composition.

In some embodiments, the polyphenol-based component is applied at a rate from about 10g a.i./ha to about 350g a.i./ha preferably 40g a.i./ha to about 90g a.i./ha.

In some embodiments, the polyphenol-based component is applied at a rate about 90g a.i./ha In some embodiments, the flumetylsulforim is applied at a rate from about 1 g/Ha – 500 g/Ha, sometimes 100g a.i./ha to about 300g a.i./ha sometimes 120g a.i./ha to about 250g a.i./ha..

In some embodiments flumetylsulforim as component (2) content is applied at a rate of from g/Ha – 500 g/Ha selected from the group including, from 5 g/ha to 120 g/ha; from 1 g/ha to 1g/ha; from 15 g/ha to 100 g/ha;from 1 g/ha to 75 g/ha; from 1 g/ha to 50 g/ha; from 1 g/ha to g/ha; from 1 g/ha to 15 g/ha:from 2 g/ha to 13 g/ha; from 5 g/ha to 10 g/ha; from 15 g/ha to 1g/ha; about 5 g/ha; about 6.25 g/ha; about 10 g/ha; about 12.5 g/ha;about 15 g a.i./ha; about g/ha; about 100 g/ha; about 125 g/ha;about 150 g/ha; about 300 g/ha; and about 500 g/ha.

Some examples of combinations may be illustrated by: flumetylsulforim 75g ai/Ha + Polyphenol 52.5 g ai/Ha flumetylsulforim 100 g ai/Ha + Polyphenol 52.5g ai/Ha flumetylsulforim 125 g ai/Ha Polyphenol 52.5 g ai/Ha flumetylsulforim 100 g ai/Ha Polyphenol 52.5 g ai/Ha flumetylsulforim 75 g ai/Ha Tebuconazole 80 Polyphenol 52.5 g ai/Ha flumetylsulforim 100 g ai/Ha + Tebuconazole 100 g ai/Ha +Polyphenol 52.5 g ai/Ha.

When the compound of component (2) and polyphenols are applied in the form of the combinations, mixtures or compositions disclosed herein, the rate at which the combinations, mixture and / or composition is applied will depend upon the particular type of fungus to be controlled, the degree of control required and the timing and method of application. In typical applications, the combinations, mixtures or compositions described herein can be applied at an application rate of between about 1 gram per hectare (g/ha ) and about 2600 g/ha active ingredient [g a.i./ha].

In some embodiments, the combination, mixture, or composition of the present disclosure is applied at a rate from about 40g a.i./ha to about 600g a.i./ha. In some embodiments, the combination, mixture, or composition is applied at a rate from about 100 g a.i./ha to about 200 g a.i./ha. In some embodiments, the combination, mixture, or composition is applied at a rate from about 100 g a.i./ha to about 130 g a.i./ha.

The components of the combination, mixture or composition of the present disclosure can be applied either separately or as part of a multipart fungicidal system. The components of the combination, mixture or composition of the present disclosure can be applied either separately or as part of a multipart fungicidal system. Consequently, the methods and uses disclosed herein include preparation of the combination, mixture, and composition from the component parts prior to application or use.

In some embodiments, the components of the combination, mixture or composition of the present disclosure are applied simultaneously.

In some embodiments, the components of the combination, mixture or composition of the present disclosure are applied contemporaneously.

In some embodiments, the components of the combination, mixture or composition of the present disclosure are applied as a succession application.

In some embodiments, components of the combination, mixture or composition of the present disclosure are applied at least one time during a growth season.

In some embodiments, applying together according to the invention refers to simultaneously, contemporaneously and /or succession application.

In some embodiments, the components of the mixture or composition of the present disclosure are applied one or more times during a growth season.

In some embodiments, the components of the combination, mixture or composition of the present disclosure are applied as a soil application. In some embodiments, the mixtures and/or compositions described herein are applied as a foliar application. In some embodiments, the components of the mixture or the composition thereof are applied as seed treatment.

In some embodiments, the components of the combination, mixture or composition of the present disclosure are applied as a soil application, as a foliar application, as seed treatment and any combination thereof.

In some embodiments, the combination, mixture, or composition of the present disclosure is applied at least one time during a growth season.

In some embodiments, the combination, mixture, or composition of the present disclosure is applied one or more times during a growth season. In some embodiments, the combination, mixture, or composition described herein are applied as a soil application. In some embodiments, the combination, mixture, or composition described herein are applied as a foliar application.

In some embodiments, controlling refers but is not limited to curative treatment, preventive treatment, persistence treatment and any combination thereof.

In some embodiments, the method of controlling is a curative treatment.

In some embodiments, the method of controlling is a preventive treatment.

In some embodiments, the method of controlling is a persistence treatment.

Application can be before or after the infection by harmful fungi and/or bacteria.

The rate at which the mixture disclosed herein is applied depends upon the particular type of fungus and/or bacteria to be controlled, the degree of control required and the timing and method of application. In general, the mixture or composition described herein can be applied at an application rate of between about 1 grams per hectare (g/ha) and about 2600 g/ha.

In some embodiments, the mixture of the present invention is applied at a rate between 0.1-100g a.i./ha this extremely wide range reflects the inclusion of extremely concentrated commercial products as well as extremely dilute point of use compositions. In some embodiments, the mixture of the present invention is applied at a rate between 50-2000 g a.i./ha (grams of active ingredient per hectare). In some embodiments, the mixture of the present invention is applied at a rate between 100-750 g a.i./ha.

In some embodiments, the mixture of the present invention, if applied as seed treatment, is to be applied at a rate between 2g per 100kg to 400 g per 100 kg of seed. In some embodiments, the mixture of the present invention, if applied as seed treatment, is to be applied at a rate between 2.5g per 100kg to 50 g per 100 kg of seed. In some embodiments, the mixture of the present invention, if applied as seed treatment, is to be applied at a rate between 2.5g per 100kg to 25 g per 100 kg of seed.

In some embodiments, the mixture of the present invention, if applied as soil application, is to be applied at a rate between 0.1 to 10,000 g/ha. In some embodiments, the mixture of the present invention, if applied as soil application, is to be applied at a rate between 1 to 5000 g/ha.

In some embodiments, the mixture is a tank mix. Any of the combinations described herein may be in the form of a tank mix. In some embodiments, each of the polyphenol-based component and additional pesticide/fungicide are formulated in its own composition prior to tank mix.

In general, inventors have found that when polyphenol-based component is added to a composition comprising fungicides it is possible to reduce the amounts of fungicidal active ingredients by between 10% and 50% and in some cases even more. Typically, the reduction of fungicides can be between about 20% and 40% without loss of efficacy and often with increased efficacy and/or performance.

As illustrated later, several compositions comprising flumetylsulforim and polyphenol-based component (polyphenols) are tested in field trials against pathogenic or otherwise unwanted fungi in crops and are compared to a product that contains flumetylsulforim, but without the polyphenols. Several tested combinations may include additional pesticidally active compounds too.

Superior fungicidal efficacy on such unwanted fungi is achieved when polyphenol-based component is added to a composition of the same doses of flumetylsulforim, and equivalent fungicidal efficacy could be achieved with much lower dosing of flumetylsulforim in the treatments that would include the Polyphenol-based component.

Trials may be conducted to assess the combinations specific polyphenol compounds as component (1) with 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one (compound of Formula I), as component (2) in fruits and vegetables selected from cereals, e.g. wheat, barley, rye, oats, rice, sorghum and the like; beets, e.g. sugar beet and fodder beet; pome and stone fruit and berries, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries; leguminous plants, e.g. beans, lentils, peas, soy beans; oleaginous plants, e.g. rape, mustard, poppy, olive, sunflower, coconut, castor-oil plant, cocoa, ground-nuts; Cucurbitaceae, e.g. pumpkins, gherkins, melons, cucumbers, squashes; fibrous plants, e.g. cotton, flax, hemp, jute; citrus fruit, e.g. orange, lemon, grape- fruit, mandarin; tropical fruit, e.g. papaya, passion fruit, mango, carambola, pineapple, banana; vegetables, e.g. spinach, lettuce, asparagus, brassicaceae such as cabbages and turnips, carrots, onions, tomatoes, potatoes, hot and sweet peppers; laurel-like plants, e.g. avocado, cinnamon, camphor tree; or plants such as maize, tobacco, nuts, coffee, sugar-cane, tea, grapevines, hops, rubber plants, as well as ornamental plants, e.g. cut flowers, roses, gerbera and flower bulbs, shrubs, deciduous trees and evergreen trees such as conifers. Advantages in cereal crops including barley and wheat are expected to be pronounced.

Further, equivalent fungicidal efficacy is achieved with all the fungicidal compounds in the compositions being able to be reduced by between 20% and 40% as may be seen in future results comparing the application of volumes exemplified by comparing the application of 1.8 L/Ha of the compositions to application of 2L/Ha and 2.2 L/Ha.

Additionally, it will be apparent that adding polyphenol-based component to fungicidal compositions comprising flumetylsulforim will result in the added benefits of lower defoliation and significantly higher yields in terms of tons of grains per hectare (where the crop is a grain crop), in at least one trial given our work in this concept it is not implausible to have of the order/magnitude of an increase from about 4800 kg/ha to about 5000 kg/ha (estimate based on potential yield per trial area).

It is additionally expected based on our research, that more and greener leaves will be found on the crop plants when polyphenol is added to the flumetylsulforim even at lower rates of application than were previously considered fungicidally effective and this effect is likely more pronounced when applied at the same concentration at the same rate of application as is typical for flumetylsulforim.

Without being bound by theory, expected greener more abundant leaves may be connected to the higher rates of efficacy against unwanted though present fungal infections combined with an anti-stress and bio stimulant effect of the polyphenol-based components over and above their efficacy boosting potential.

It may be that the polyphenol compound will be found to be beneficial to plants when applied alone, this of course is an added benefit which itself is not insignificant.

Similarly, it is predicted that addition of even small amounts of copper-based compounds will significantly improve efficacy even when flumetylsulforim is reduced by 25% or more.

None of the treatments is expected to result in phytotoxicity (which can be evaluated by visual inspection).

In the treatments, the compositions are applied from a spray mixture including for example, 0.L/ha of commercial adjuvant, Rumba® which comprises 765g/L Methyl Soyate. Thus, the applied Methyl Soyate can often be 191.25 g/L for each treatment application.

In embodiments, the combinations or mixtures of the present invention may be formulated as one composition. The combinations of the present invention may be formulated as separate compositions. The combinations of the present invention may be formulated in more than one composition.

In embodiments the combinations of the present invention may be formulated as separate compositions. The composition of the polyphenol-based component (1) of the present inventive combination may be formulated and provided together with preparative instructions or otherwise adapted for combination with a separate, conceivably, commercially available composition of the fungicide(s) of component (2) exemplified by flumetylsulforim.

In embodiments the combinations of the present invention may be formulated as separate compositions. The composition of the polyphenol-based component (1) of the present inventive combination may be formulated and provided together with preparative instructions or otherwise adapted for combination with a separate, conceivably, commercially available composition of the fungicide(s) of component (2) exemplified by flumetylsulforim and the additional fungicides of component (3).

In embodiments the combinations of the present invention may be formulated as separate compositions. The composition of the polyphenol-based component (1) together with an additional pesticide compound of component (3), of the present inventive combination may be formulated and provided together with preparative instructions or otherwise adapted for combination with separate, conceivably, commercially available composition(s) of the fungicide(s) of component (2) exemplified by flumetylsulforim.

In embodiments the combinations of the present invention may be formulated as separate compositions. The composition of the polyphenol-based component (1) together with an additional pesticide compound of component (3), of the present inventive combination may be formulated and provided together with preparative instructions or otherwise adapted for combination with separate, possibly, commercially available composition(s) of the fungicide(s) of component (2) exemplified by flumetylsulforim, in admixture with the additional fungicide(s) of component (3).

In embodiments the combinations of the present invention may be formulated as separate compositions. The composition of the polyphenol-based component (1) together with the additional fungicide of component (3), of the present inventive combination may be formulated and provided together with preparative instructions or otherwise adapted for combination with separate, possibly, commercially available composition(s) of the fungicide(s) of component (2) exemplified by flumetylsulforim.

In embodiments the present invention also provides a fungicidal composition comprising any one of the combinations disclosed herein, and an agriculturally acceptable carrier.

In embodiments the present invention also provides fungicidal composition(s) for the combinations comprising any one of the combinations disclosed herein, and an agriculturally acceptable carrier.

In some embodiments, the combination comprises a composition. Any of the combinations described herein may be in the form of a composition.

In embodiments the combination, mixture or composition comprising the polyphenol-based component and at least one fungicide exemplified by flumetylsulforim may be an improved combination, mixture, or composition in any one or any combination of ways as described below.

In some embodiments, the combination comprises an amount of polyphenol-based component and an amount of at least one fungicide exemplified by flumetylsulforim. The combination comprising polyphenol-based component and at least one fungicide of component (2) may be an improved combination in any one or any combination of ways as described below.

In some embodiments, improving plant development comprises enhancing shoot of the plant. In some embodiments, enhancement in shoot is measured by shoot weight. In some embodiments, shoot weight is increased by at least 1%, 5%, 10, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.

In some embodiments, improving plant development comprises enhancing plant vigor. In some embodiments, plant vigor is assessed using the relative vigor index. In some embodiments, plant vigor is increased by at least 1%, 5%, 10, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.

In some embodiments, improving plant development comprises enhancing greening effect on leaves. In some embodiments, greening effect on leaves is assessed using the relative vigor index. In some embodiments, greening effect on leaves is increased by at least 1%, 5%, or 10%.

In some embodiments, improving plant development comprises enhancing plant yield. In some embodiments, plant yield is increased by at least 1%, 5%, 10, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100% or more, or each and any intermediate value.

In some embodiments, the combination comprises an improved combination in that it has improved potentiated efficacy, improved long lasting effect, improved green leaf area, improved greening effect, increased spectrum of disease activity, increased efficacy against disease not controlled by the solo fungicides, higher plant/crop yield, higher plant/crop protein content, higher plant/crop sugar content, higher plant/crop °Brix level, better color grading of fruits, higher thousand kernels weight, higher test weight or hectoliter weight, increased fruit size, increased number of marketable fruits, improved plant vigor, and/or reduced risks of adverse effects on plants as compared with use of exemplified by flumetylsulforim absent polyphenol compounds.

The fungal pathogen to be addressed by the combinations and methods herein disclosed can be one or more of Alternaria species on vegetables, oilseed rape, sugar beet and rice, such as, A. solani in tomatoes or A. cucumerina in cucumber or melon; Aphanomyces species on sugar beet and vegetables; Ascochyta species on cereals, legumes and vegetables; Bipolaris and Drechslera species on corn, cereals, rice and lawns, for example, D. maydis on corn; Blumeria graminis (powdery mildew) on cereals; Botrytis cinerea (gray mold) on strawberries, vegetables and flowers or B. aclada on onion; Bremia lactucae on lettuce; Cercospora species on corn, soybeans, rice, sugar beet and coffee as C. beticola in sugarbeet or C. kikuchii in soybean; Cladosporium species on several crops; Claviceps purpurea on rye; Cochliobolus species on corn, cereals, rice, for example Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice; Colletotricum species on vegetables, soybeans and cotton, such as Colletotrichum truncatum in pepper and soybean; Drechslera species and Pyrenophora species on corn, cereals, rice and lawns, for example, D. teres on barley or D. tritici-repentis on wheat; Esca on grapevines, caused by Phaeoacremonium chlamydosporum, P. Aleophilum and Fomitiporia punctata (syn. Phellinus punctatus), Exserohilum species on corn; Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumbers; Fusarium and Verticillium species on various plants, for example, Fusarium graminearum or Fusarium culmorum on cereals or F. oxysporum on a multitude of plants, such as, for example, tomatoes; Gaeumannomyces graminis on cereals; Gibberella species on cereals and rice (for example Gibberella fujikuroi on rice); Grainstaining complex on rice; Helminthosporium species on corn and rice; Hemileia vastatrix on coffee; Microdochium nivale on cereals; Mycosphaerella species on several crops, for example, M. brassicicola on brassicas; Parastagonospora nodorum on cereals; Peronospora species on cabbages, legumes and bulbous plants, for example, P. brassicae on cabbage or P. destructor on onions; Phakopsora pachyrhizi and Phakopsora meibomiae on soybeans; Phoma species on soybean, cucurbits, tomato and brassicas; Phomopsis species on soybeans, sunflowers and grapes; Phytophthora infestans on potatoes and tomatoes; Phytophthora species on various plants, for example, P. capsici on bell pepper, P. citrophthora and P. citricola in citrus; Plasmopara viticola on grapevines; Pleosporales on various plants, for example, Pleospora herbarum in alfalfa, tomato and chickpeas; Pseudocercosporella herpotrichoides on cereals; Pseudoperonospora on various plants, for example, P. cubensis on cucumber or P. humili on hops; Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae on rice; Pyricularia grisea on lawns and cereals; Pythium spp. on lawns, rice, corn, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants, for example, P. ultimum on various plants, P. aphanidermatum on lawns; Ramularia species on cereals, barley and cotton, for example, Ramularia collo-cygni on barley and Ramularia areola on cotton; Rhizoctonia species on cotton, rice, potatoes, lawns, corn, oilseed rape, sugar beet, vegetables and on various plants, for example, R. solani on beet and various plants; Rhynchosporium secalis on barley, rye and triticale; Sclerotinia species on oilseed rape, sunflowers and lettuce; Septoria species on several crops as S. lactucae in lettuce; Erysiphe species on wheat such as Erysiphe graminis; Erysiphe (syn. Uncinula) necator on grapevines; Setosphaeria species on corn and lawns; Sphacelotheca reiliana on corn; Thielaviopsis species on soybeans and cotton; Tilletia species on cereals; Ustilago species on cereals, corn and sugar cane, for example, U. maydis on corn. Cercospora kikuchii on soybean; Septoria glycines (Late Season diseases) on soybean; Corynespora cassiicola(target Spot) on soybean; Microsphaera difusa (Powder Mildew) on soybean; Colletotrichum truncatum(Antrachnosis) on soybean Colletotrichum truncatum on soybean; Sclerotinea sclerotiorum(White mold) on soybean. Puccinia kuehnii(orange rust) on sugarcane; C. paradoxa(pineapple rot) on sugar cane.

In some embodiments, the fungal pathogen group is Hyponectriaceae. In some embodiments, the fungal pathogen group is Phyllostictaceae. In some embodiments, the fungal pathogen group is Mycosphaerellaceae. In some embodiments, the fungal pathogen group is Ceratobasidiaceae. In some embodiments, the fungal pathogen group is Erysiphaceae. In some embodiments, the fungal pathogen group is Trichocomaceae. In some embodiments, the fungal pathogen group is Sclerotiniaceae. In some embodiments, the fungal pathogen group is Dermateaceae. In some embodiments, the fungal pathogen group is Sclerotiniaceae. In some embodiments, the fungal pathogen group is Nectriaceae. In some embodiments, the fungal pathogen group is Peronosporaceae. In some embodiments, the fungal pathogen group is Glomerellaceae. In some embodiments, the fungal pathogen group is Pleosporaceae. In some embodiments, the fungal pathogen group is Leptosphaeriaceae. In some embodiments, the fungal pathogen group is Venturiaceae. In some embodiments, the fungal pathogen group is Didymellaceae. In some embodiments, the fungal pathogen group is Pleosporaceae. In some embodiments, the fungal pathogen group is Corynesporascaceae. In some embodiments, the fungal pathogen group is Pucciniaceae. In some embodiments, the fungal pathogen group is Chaconiaceae. In some embodiments, the fungal pathogen group is Phakopsoraceae. In some embodiments, the fungal pathogen group is Pucciniaceae. In some embodiments, the fungal pathogen group is Magnaporthales. In some embodiments, the fungal pathogen group is Taphrinaceae. In some embodiments, the fungal pathogen group is Ustilaginaceae.

In some embodiments, the pathogen class is Amphisphaeriales. In some embodiments, the pathogen class is Botryosphaeriales. In some embodiments, the pathogen class is Capnodiales. In some embodiments, the pathogen class is Ceratobasidiales. In some embodiments, the pathogen class is Erysiphales. In some embodiments, the pathogen class is Eurotiales. In some embodiments, the pathogen class is Helotiales. In some embodiments, the pathogen class is Hypocreales. In some embodiments, the pathogen class is Peronosporales. In some embodiments, the pathogen class is Phyllachorales. In some embodiments, the pathogen class is Pleosporales. In some embodiments, the pathogen class is Pucciniales. In some embodiments, the pathogen class is Pyriculariaceae. In some embodiments, the pathogen class is Taphrinales. In some embodiments, the pathogen class is Ustilaginales.

In some embodiments, the fungal pathogen is Botrytis cinerea. In some embodiments, the fungal pathogen is Microdochium sp. In some embodiments, the fungal pathogen is Phyllosticta ampelicida. In some embodiments, the fungal pathogen is Mycosphaerella fijiensis. In some embodiments, the fungal pathogen is Zymoseptoria tritici. In some embodiments, the fungal pathogen is Ramularia collo-cygni. In some embodiments, the fungal pathogen is Cercospora zeae-maydis. In some embodiments, the fungal pathogen is Ramularia areola. In some embodiments, the fungal pathogen is Cercospora beticola. In some embodiments, the fungal pathogen is Ramularia beticola. In some embodiments, the fungal pathogen is Rhizoctonia solani / Thanatephorus cucumeris. In some embodiments, the fungal pathogen is Blumeria graminis. In some embodiments, the fungal pathogen is Erysiphe cichoracearum. In some embodiments, the fungal pathogen is Sphaerotheca fuliginea. In some embodiments, the fungal pathogen is Erysiphe necator. In some embodiments, the fungal pathogen is Podosphaera macularis. In some embodiments, the fungal pathogen is Podosphaera leucotricha. In some embodiments, the fungal pathogen is Leveillula Taurica. In some embodiments, the fungal pathogen is Oidium neolycopersici. In some embodiments, the fungal pathogen is Erysiphe betae. In some embodiments, the fungal pathogen is Erysiphe polygoni. In some embodiments, the fungal pathogen is Aspergillus sp. In some embodiments, the fungal pathogen is Botrytis cinerea. In some embodiments, the fungal pathogen is Pyrenopeziza brassicae. In some embodiments, the fungal pathogen is Sclerotinia sclerotiorum. In some embodiments, the fungal pathogen is Botrytis cinerea. In some embodiments, the fungal pathogen is Monilinia spp. In some embodiments, the fungal pathogen is Monilinia laxa. In some embodiments, the fungal pathogen is Monilia fructigena. In some embodiments, the fungal pathogen is Monilia fructicola. In some embodiments, the fungal pathogen is Fusarium sp. In some embodiments, the fungal pathogen is Phytophthora sp. In some embodiments, the fungal pathogen is Phytophthora palmivora. In some embodiments, the fungal pathogen is Phytophthora megakarya. In some embodiments, the fungal pathogen is Phytophthora capsica. In some embodiments, the fungal pathogen is Pseudoperonospora cubensis. In some embodiments, the fungal pathogen is Plasmopara viticola. In some embodiments, the fungal pathogen is Pseudoperonospora humul. In some embodiments, the fungal pathogen is Phytophthora infestans. In some embodiments, the fungal pathogen is Peronospora viciae. In some embodiments, the. fungal pathogen is Phytopthora sp. In some embodiments, the fungal pathogen is Phytophthora infestans. In some embodiments, the fungal pathogen is Colletotrichum kahawae. In some embodiments, the fungal pathogen is Colletotrichum sp .. In some embodiments, the fungal pathogen is Pyrenophora tritici-repentis In some embodiments, the fungal pathogen is Drechslera tritici-repentis. In some embodiments, the fungal pathogen is Pyrenophora teres. In some embodiments, the fungal pathogen is Setosphaeria turcica. In some embodiments, the fungal pathogen is Cochliobolus heterostrophus. In some embodiments, the fungal pathogen is Cochliobolus carbonum. In some embodiments, the fungal pathogen is Alternaria spp. In some embodiments, the fungal pathogen is Alternaria cucumerina. In some embodiments, the fungal pathogen is Plenodomus lingam. In some embodiments, the fungal pathogen is Alternaria alternate. In some embodiments, the fungal pathogen is Pleospora allii. In some embodiments, the fungal pathogen is Alternaria mali. In some embodiments, the fungal pathogen is Alternaria sp. In some embodiments, the fungal pathogen is Venturia inaequalis. In some embodiments, the fungal pathogen is Venturia pyrina. In some embodiments, the fungal pathogen is Alternaria sp . In some embodiments, the fungal pathogen is Ascochyta rabiei. In some embodiments, the fungal pathogen is Alternaria sp . In some embodiments, the fungal pathogen is Corynespora cassiicola. In some embodiments, the fungal pathogen is Puccinia recondite. In some embodiments, the fungal pathogen is Puccinia triticina. In some embodiments, the fungal pathogen is Hemileia vastatrix. In some embodiments, the fungal pathogen is Phakopsora pachyrhizi. In some embodiments, the fungal pathogen is Uromyces betae. In some embodiments, the fungal pathogen is Pyricularia oryzae. In some embodiments, the fungal pathogen is Taphrina spp. In some embodiments, the fungal pathogen is Taphrina deformans. In some embodiments, the fungal pathogen is Ustilago maydis.

Methods of using the inventive Combination comprise uses for controlling fungal groups, fungal classes, and fungal pathogens, including the fungal groups, fungal classes and fungal pathogens described herein.

Fungal infection may cause fungal disease affecting the plant or soil. In some embodiments, the invention comprises treating a plant or soil against fungal infection comprising treating the plant or soil against fungal disease with the inventive combination(s).

In some embodiments, the fungal disease is apple scab disease. In some embodiments, the fungal disease is seedling blight. In some embodiments, the fungal disease is foliar & ear disease. In some embodiments, the fungal disease is Black rot. In some embodiments, the fungal disease is Black sigatoka. In some embodiments, the fungal disease is Septoria. In some embodiments, the fungal disease is Ramularia leaf spot. In some embodiments, the fungal disease is gray leaf spot. In some embodiments, the fungal disease is leaf spot of beet. In some embodiments, the fungal disease is sheath blight. In some embodiments, the fungal disease is powdery mildew. In some embodiments, the fungal disease is Aspergillus ear rot. In some embodiments, the fungal disease is grey mold. In some embodiments, the fungal disease is Sclerotinia. In some embodiments, the fungal disease is Monilia. In some embodiments, the fungal disease is Fusarium head blight. In some embodiments, the fungal disease is Maize Ear and Kernel Rot. In some embodiments, the fungal disease is Crown and root rot. In some embodiments, the fungal disease is Black pod. In some embodiments, the fungal disease is Downy mildew. In some embodiments, the fungal disease is Late blight. In some embodiments, the fungal disease is Coffee Berry Disease. In some embodiments, the fungal disease is Anthracnose. In some embodiments, Antracnose. In some embodiments, the fungal disease is yellow spot. In some embodiments, the fungal disease is Net blotch. In some embodiments, the fungal disease is Northern Corn Leaf Blight. In some embodiments, the fungal disease is Northern Corn Leaf Spot. In some embodiments, the fungal disease is Phoma stem canker and leaf spot. In some embodiments, the fungal disease is Alternaria. In some embodiments, the fungal disease is Brown spot of pear. In some embodiments, the fungal disease is Alternaria blotch of apple. In some embodiments, the fungal disease is scab. In some embodiments, the fungal disease is Early blight. In some embodiments, the fungal disease is Didymella pisi. In some embodiments, the fungal disease is Target spot. In some embodiments, the fungal disease is Brown rust. In some embodiments, the fungal disease is yellow rust. In some embodiments, the fungal disease is Coffee Leaf Rust. In some embodiments, the fungal disease is Asian soybean rust. In some embodiments, the fungal disease is Rust. In some embodiments, the fungal disease is Rice Blast. In some embodiments, the fungal disease is leaf curl. In some embodiments, the fungal disease is Common Smut.

Additional fungicide is used for controlling broad spectrum of diseases, including the fungal diseases described herein. Additional fungicide may be used on a variety of plants, including the plants described herein. Preferably, additional fungicide is used for controlling the following fungal diseases. In some embodiments, the disease is Sheath blight in rice crop. In some embodiments, the disease is apple scab. In some embodiments, the disease is Early blight disease in vegetable crop. In some embodiments, the vegetable crop is potato. In some embodiments, the vegetable crop is tomato. In some embodiments, the vegetable crop is chili. In some embodiments, the disease is Anthracnose and/or Alternaria. In some embodiments, the disease is an early blight disease in potatoes. In some embodiments, the disease is an anthracnose disease in chili. In some embodiments, the disease is Septoria in cereals. In some embodiments, the disease is black sigatoka in banana. In some embodiments, the disease is Sphaerotheca fuliginea in melon. In some embodiments, the disease is Anthracnose and/or Alternariain chilli. In some embodiments, the disease is Erysiphe necator in grape. In some embodiments, the disease is Phakopsora pachyrhizi in soybean. In some embodiments, the disease is Botrytis cinerea in strawberry. In some embodiments, the disease is Venturia inaequalis in apple. In some embodiments, the disease is Alternaria sp. or Phytophthora infestans in tomato. In some embodiments, the disease is Plasmopara viticola in grape. In some embodiments, the disease is caused by Colletotrichum capsica. In some embodiments, the disease is caused by Alternaria solani.

Each embodiment disclosed herein is contemplated as being applicable to each of the other disclosed embodiments. Thus, all combinations of the various elements described herein are within the scope of the invention. In addition, the elements recited in the composition embodiments can be used in the combination, mixture (including synergistic mixture), package, method and use embodiments described herein and vice versa. In addition, the elements recited in the combination embodiments can be used in the composition, kit, method and use embodiments described herein and vice versa.

The following representative examples illustrate the practice of the present invention in some of its embodiments but should not be construed as limiting the scope of the invention in any way. At this initial stage these so-called examples are only for illustrative purposes, none of the specific text of any examples below should be seen as evidence that the various trials have as yet been conducted to full completion or for that matter that results are currently available. Other embodiments will be apparent to one skilled in the art from consideration of the specification and examples. It is intended that the specification, including the examples, is considered exemplary and/or illustrative only, without limiting the scope and coverage of the invention.

A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components.

It is often understood that the term "synergy" is as defined by Colby S. R. in an article entitled "Calculation of the synergistic and antagonistic responses of herbicide combinations" published in the journal Weeds, 1967, 15, p. 20-22 The action expected for a given combination of one active components can be calculated as follows: ? = ? + ? −??100 The action expected for a given combination of three active components can be calculated as follows: ? = ? + ? + ? −?? + ?? + ??100+ ??? 10000 in which E represents the expected effect, e.g., percentage of pest control, for the combination of the active ingredients at defined doses (for example equal to x and y respectively), X is the effect, e.g., percentage of pest control, observed for compound (I) at a defined dose (equal to x), Y is the effect, e.g., percentage of pest control, observed for compound (II) at a defined dose (equal to y). Here, efficacy or percent inhibition is determined in %. 0% means efficacy that corresponds to the Control, i.e., as if no treatment had been applied. Whereas a percent inhibition of 100% means that complete control is observed. When the percent control observed for the combination is greater than E, there is a synergistic effect. When the percent control observed for the combination is equal to E, there is an additive effect and wherein the percent control observed for the combination is lower than E, there is an antagonistic effect.

In some embodiments, the combination is synergistic for controlling pathogen. In some embodiments, the combination is synergistic for enhancing crop plant. In some embodiments, the combination is synergistic for enhancing plant development. In some other embodiments, the combination is synergistic for enhancing root system. In some embodiments, the combination is synergistic for improving plant quality. In some embodiments, the combination is synergistic for regulating plant growth. In some embodiments, the combination is synergistic for controlling different species of pathogen.

While the present disclosure of the invention may be susceptible to various modifications and alternative forms, specific embodiments have been described by way of example in detail herein. However, it is understood that the present disclosure is not intended to be limited to the particular forms disclosed. Rather, the present disclosure is to cover all modifications, equivalents, and alternatives falling within the scope of the present disclosure as defined by the following claims and their legal equivalents.

In some useful embodiments, when assessing the optimum component (1) polyphenol-based content, it might be practical to start with an amount of the polyphenol compound that is up to about 10% of the total weight of the composition of the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide composition (2) intended for enhancement.

Typically, the enhancement is of the efficacy of 5-fluoro-4-imino-3-methyl-1-tosyl-3,dihydropyrimidin-2(1H)-one compositions.

ILLUSTRATIVE NON LIMITING EXAMPLES As mentioned the present invention relates to fungicidal combinations comprising at least two components: polyphenol-based component (1) and at least one fungicide component (2) selected from the group of N3-substituted-N1-sulphonyl-5-fluoropyrimidine compounds, and in particular 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one, a compound of Formula I .

As mentioned, the pesticidal, typically, fungicidal combinations of the inventions can, in certain embodiments further comprise one or more additional pesticidal compounds as component (3). The invention can enable a reduction in the amounts of additional pesticidal compounds used together with fungicides or even eliminate the need for their use, often resulting in equivalent or superior fungicidal activity or performance.

In several embodiments the pesticidal, typically, fungicidal combinations of the inventions can, in certain embodiments further comprise additional pesticidally active component(s) as detailed elsewhere in this disclosure or even simply efficacy or performance enhancing adjuvants.

The exact composition or formulation type for practicing the present invention is not vital as this invention relates to the interaction of polyphenol compounds of component (1) with the fungicide component (2) exemplified by the compound of formular I above, and sometimes with the additional fungicides of component (3). While non-pesticidal ingredients and the type of delivery system or composition, can of course have an effect on the degree of improvement achieved by the invention, the invention is not considered to be dependent on a particular formulation type or vehicle or pesticidally inactive component other than those components mentioned above.

Clearly though when comparing compositions, it is most useful to compare like with like for comparative purposes it is often useful to compare the effects of a particular composition of compounds of formula I with exactly the same composition that includes a polyphenol compound of component (1).

FIELD TRIALS The following trials are conducted to evaluate various advantages of combining polyphenol component (1) compounds with 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone, CAS No. 1616664-98-2.

Example For the purpose of the trials the polyphenol component (1) is obtained as a separate composition from the fungicide component (2) OD compound composition and in those experiments when they are combined, they are both combined in a spray mix or tank mix with water prior to application. It should be immediately apparent that the method of combination in a single concentrate or dilution additive should not have a plausible difference beyond formulation considerations and practicality.

In some of these particular trials a composition of polyphenol compounds is used as component (1) and an oil dispersion (OD) composition of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone as component (2) fungicide. A commercial emulsifiable concentrate of Tebuconazole is used as an additional pesticidal component. The component (2) fungicide OD composition to be used is essentially similar to example 23 of co-pending application PCT/IB2021/053762.

Fungicide Component (2) OD composition comprising the compound of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-2(1H)-pyrimidinone is sometimes referred to here as Component (2) fungicide or Compound of formula I.

The following is an illustrative method of preparation but inventors have no reason to exclude other methods of preparation or order of steps, or times, temperatures, etc.

Composition Code ADM.00050.F.3.C – non limiting illustration of a composition.

INGREDIENT IDENTITY % w/w Kg per 100L Component (2) 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one (24.51) 2 Agrimer AL-22 Vinyl pyrrolidone copolymers like alkyl grafted PVP 80% by weight of C 16 α-olefin 20% by weight of polymerized vinylpyrrolidone mw~ 7300 (2.94) Atlox 49Star Shaped Polymer - sorbitol ethoxylate ester of polymerized fatty acid Low HLB ~ 5 (4.9) Aerosol OT-SE Docusate sodium, sodium dioctyl sulfosuccinate 6 (5.88) Synperonic PE/L polyethylene oxide/polypropylene oxide block polymer mw 2900 g/mol 40% ethylene oxide content poloxamer 184, and/or CAS no. 9003-11-and/or CAS no. 106392-12-6 (5.88) Genapol X 050 Ethoxylated Iso-tridecyl Alcohol 5 (4.9) EPOXOL D65 Epoxidized soybean oil 5 (4.9) 50 Aerosil R2 Silicones and siloxanes, dimethyl-, reaction products with silica Decamethyl cyclopenta siloxane octa methyl cyclotetra siloxane 2.5 (2.46) Tween 24 L.M. Polyoxyethylene Sorbitan Fatty Acid Ester - saturated (lauric acid) (2.94) Agnique ME RD-F C 18 Methyl Canolate (C 16-18-unsaturated fatty acid methyl esters) To 100 To 100L Trials are conducted with Polyphenols, Component (1); 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one, Component (2) fungicide w/wo one or two additional Component (3) fungicides.

Trial Protocol Summary Title Component (1) Polyphenols with Component (2), w/wo additional pesticide(s) as Component (3) Pathogens Phakopsora pachyrhizi and other diseases CROP Soybean Target Soybean rust and others soybean rust /FCD phase Initial number of trials samples End of November # Treatments (Identifier) Composition Dose g a.i./ha ADF-16 (2) TBZ PCX Polyphenol (1) MCZ (3) 1 Untreated 0 0 0 0 0 2ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.30 75 3ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.40 100 4ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.50 125 ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.30 75 polyphenol (1) polyphenol composition 0.15 52.5 6 ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.40 100 polyphenol (1) polyphenol composition 0.15 52.5 7 ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.50 125 polyphenol (1) polyphenol composition 0.15 52.5 8 ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.30 75 TBZ(Bayer) Tebuconazol (250) - EC 0.32 80 9 ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.30 75 TBZ(Bayer) Tebuconazol (250) - EC 0.32 80 polyphenol (1) polyphenol composition 0.15 52.5 ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.40 100 TBZ(Bayer) Tebuconazol (250) - EC 0.40 100 11 ADM.00050.F.3.C (2) ADF 16 (250) - OD 0.40 100 TBZ(Bayer) Tebuconazol (250) - EC 0.40 100 polyphenol (1) polyphenol composition 0.15 52.5 12 TBZ(Bayer) Tebuconazol (250) - EC 0.40 100 13TBZ(Bayer) Tebuconazol (250) - EC 0.40 100 polyphenol (1) polyphenol composition 0.15 52.5 Randomized trials: 4 replications number of application: Spray volume 100 l/Ha Application time: V8/14DAT1/28DAT interval between applications: 14 days Evaluation: Efficacy/Phytotoxicity/Plant Effects/Other Observations Efficacy incidence/severity/Phytotoxicity Measured each application/7/14/21/28 days after last application Defoliation pre harvest Yield Kg/ha / yield components (weight of 1000 grains) Report Any Issues with formulation/Any Plant Observations Analysis AACPD (efficacy) / Tukey (5%) statistical analysis Samples ml Safe Margin (30%) Total SamplesADM.00050.F.3.C (2) 645 193.5 8TBZ (Tebuconazole Bayer) 288 86.4 3Rumba [Soybean Methyl ester] 1050 315 13Polyphenols composition 135 40.5 1 Separate compositions are combined in tank-mix or solo tank mix, with Rumba ® 0.5%v/v (Me Soyate). Water Volume 150 L/ha. Applications: apply at stage V8; V8+14 days; V8+28 days and apply at stage V8+42 days only if necessary according to disease pressure.

Carry out the experiment on late-planted soybeans (such as December). Conduct studies in accordance with IN 36/42, including sending the MAPA spreadsheet (by the 10th of each month) to the federation unit. Update on a monthly basis on the status of the experiment. Carry out the 4th application, only if necessary according to the pressure of the disease - Assess the presence and severity of diseases other than rust if they occur. Carry out photographic records of all treatments, aiming to verify severity, selectivity and also defoliation .

Based on the results obtained, the area under the disease progress curve (AUDPC) and respective % of control is calculated.

Example Some target pathogenic conditions for trials include Wheat Puccinia striiformis, Puccinia triticina, Blumeria graminis, Septoria tritici, Fusarium spp, Barley Puccinia hordei, Blumeria graminis, Pyrenophora teres, Rhynchosporium secalis and Ramularia collo-cygni Addressing Barley net blotch (Pyrenophora teres) and Ramularia leaf spot (Ramularia collo-cygni) on barley.

A trial is conducted of specific polyphenol compounds as component (1) with 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, such as 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one (compound of Formula I), as component (2).

It is noted that further experimental arms are conducted with and without other different pesticidal compounds e.g., fungicide compounds as components (3) and/or with or without further different pesticidal (fungicidal) ingredients. These additional trial arms are perhaps usefully based on publications including PCT/DK2016/050292 although no limitation is implied at all other than as inspiration. The crops and pathogens addressed in PCT/DK2016/050292 are useful as the basis for assessing the advantages of adding polyphenol compounds (1) to 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one (compound of Formula I), as component (2). In general, when designing the trials, it is advantageous to choose particularly low doses of 5-fluoro-4-imino-3-methyl-1-tosyl-3,4 dihydropyrimidin-2(1H)-one with or without other active fungicidal components that are not expected to be sufficiently efficacious so that the advantages of adding one or more polyphenolic components (1) is more clearly apparent.

A series of experiments are conducted to evaluate the fungicidal control of Barley net blotch (Pyrenophora teres) and Ramularia leaf spot (Ramularia collo-cygni) on barley with a compound of Formula I with or without another fungicide. The experiment is conducted by applying a compound of Formula I. The combinations and/or compositions are diluted in water for application. Further trial arms are conducted wherein further fungicides are added and compared.

Treatment list Treatment AI Rate (g AI/ha)Untreated check Component (2) From 50 to 200 g AI/ha cyanidin-3-O-glucoside From 1 to 30 g AI/ha Sesamolin From 1 to 30 g AI/ha Bisdemethoxycurcumin From 1 to 30 g AI/ha Curcumin From 1 to 30 g AI/ha Demethoxy curcumin From 1 to 30 g AI/ha [6]-Gingerol From 1 to 30 g AI/ha 2-Methoxy-5-prop-1-enylphenol From 1 to 30 g AI/ha Acetyl eugenol From 1 to 30 g AI/ha Anethole From 1 to 30 g AI/ha Estragole From 1 to 30 g AI/ha Eugenol From 1 to 30 g AI/ha Carnosic acid From 1 to 30 g AI/ha Carnosol From 1 to 30 g AI/ha Carvacrol From 1 to 30 g AI/ha Epirosmanol From 1 to 30 g AI/ha Rosmadial From 1 to 30 g AI/ha Rosmanol From 1 to 30 g AI/ha Thymol From 1 to 30 g AI/ha Tannic acid 1700MW From 1 to 30 g AI/ha Resveratrol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha cyanidin-3-O-glucoside From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Sesamolin From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Bisdemethoxycurcumin From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Curcumin From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Demethoxycurcumin From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha [6]-Gingerol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha 2-Methoxy-5-prop-1-enylphenol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Acetyl eugenol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Anethole From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Estragole From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Eugenol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Carnosic acid From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Carnosol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Carvacrol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Epirosmanol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Rosmadial From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Rosmanol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Thymol From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Tannic acid (e.g., 1700MW) From 1 to 30 g AI/ha Component (2) From 50 to 200 g AI/ha Resveratrol From 1 to 30 g AI/ha The Barley plants are sprayed with each one of the above treatments to test for fungicidal control of Barley net blotch (Pyrenophora teres) and Ramularia leaf spot (Ramularia collo-cygni) in Barley. Each of the above treatments is applied from 1 to 10 times according to the disease development, applications occurring 7-14 days after the previous one. The treatments are composed of 4 replicates. Evaluations are performed for the whole duration of the experiment.

As regards possible compositions of component (2) fungicides [5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one], examples of various types of composition ingredients are discussed in PCT application PCT/IB2020/056828 which may be useful for preparing compositions according to the invention in order to test the advantages on the inventive combinations. Incorporated here as regards the composition ingredients and preparation only.

We note that recently published application PCT/IB2023/052005, hereby incorporated as regards 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one compositions and preparation, includes a suspension concentrate composition of the compound of formula I and we see no reason why similar compositions should not be useful vehicles for comparing compositions of a component (2) compound exemplified by 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one,with and without component (3) additional pesticidal compounds as compared with the inclusion of polyphenol compounds of component (1). It should be made very clear however that the instant invention is in no way limited by the vehicle, composition, type used, although of course composition and formulation skills will be useful in optimizing the composition embodiments however they are well within the skills of formulators in this field.

The methods of preparing some illustrative compositions are also to be found in the referenced applications referred to and ordinarily formulators will adjust the relative contents of these to include the Polyphenol compounds readily.

An illustration of a vehicle for testing and comparing component (2) combinations with and without Component (1) Polyphenol compounds, can be based on the disclosure of PCT/IB2023/052005, the contents of which are hereby included in its entirety only as pertains to the compositions and methods of preparations.

When testing the combinations of the invention it is possible to take an exemplary concentrated composition and dilute it in a spray tank with water to the ready to spray concentration with or without the polyphenol compounds component (2) either prepared as part of the concentrate or added to the tank-mix. In a similar fashion the additional different pesticidal component (3) compounds (if included) are also included either as components prepared in the concentrate or as separately prepared or obtained compositions all as described generally above.

The illustrative compositions that can be used to test the advantages of the inventive compositions can be based on the compositions as illustrated in pending application No. PCT/1B2019/0594claiming priority to US 62/755,866 the contents of which are hereby included in its entirety as regards composition and method of preparation. These compositions are only illustrative and no intention to limit the invention to these compositions or even the type of composition, although, useful for formulation directions.

The illustrative compositions can be based on the compositions as illustrated in pending Argentinian patent application No. 20230101145 claiming priority to US 63/339,982 incorporated herein as regards compositions and methods of preparations. These compositions are only illustrative and no intention to limit the invention to these compositions or even the type of composition, although, although they are useful for formulation directions, in preparing compositions comprising the combinations of the invention.

In general, the inclusion of the polyphenol-based component can allow for reduction of all fungicide components in the combinations by about 10-50% without significant loss of fungicidal efficacy as well as plant health related benefits.

It is shown in trials that, when polyphenol-based component is included/used, it is possible to reduce the rate of application of all the fungicides in the tested combinations by between 20 and % which will be seen when comparing the efficacy of composition that are sprayed e.g., at 1.L/Ha to those applied at 2.0L and 2.2 L/Ha in one specific illustrative example.

RESULTS AND DISCUSSION It is expected that the fungicide treatments applications do not cause visual symptoms of phytotoxicity to soybean plants, as observed visually.

The first two applications of the fungicide treatments are generally carried out preventively, without the presence of symptoms of Asian rust in soybean plants. In the evaluation prior to the third application, the first symptoms of the disease are detected in the experiment, but only in the control treatment, without application of fungicides. In the next evaluation, prior to the fourth application, the disease is already present in all treatments and with significantly higher severity in the control without controlling pesticide, with no difference between the fungicides being tested.

In severity assessments, being performed at 7, 14, 21 and 28 DAA4, Asian Soybean Rust is expected to evolve rapidly and a greater differentiation between treatments with regard to control efficiency is expected. In general, a superior performance of all treatments compared to the commercial product is expected, and this effect is expected to be clearly significant at 7 and DAA4. Sometimes the treatments are dose related.

The AUDPC and defoliation data will confirm the results and show high control efficiency in all fungicide treatments, with a reduction of the order of about 80%.

All treatments with fungicide application produces more disease control than the untreated control.

Claims (22)

1. Claims 1) A polyphenol-based compound for use as pesticidal and/or fungicidal enhancement agent, for enhancing the efficacy and/or performance of N3-substituted-N1-sulphonyl-5-fluoropyrimidine pesticidal compounds and/or their derivatives.

2. A polyphenol-based compound for use as fungicidal and/or performance enhancement agent, for enhancing the efficacy and/or performance of 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicidal compounds and/or their derivatives.

3. A polyphenol-based compound for use as a performance enhancement agent, for enhancing the performance of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one or derivatives thereof.

4. The polyphenol-based compound for use as pesticidal, fungicidal and/or performance enhancement agent of any one of claims 1-2 characterized by reduced deleterious environmental impact as compared with the use of non-polyphenol-based pesticidally active pesticidal, fungicidal or performance enhancement agents.

5. A combination of N3-substituted-N1-sulphonyl-5-fluoropyrimidine pesticidal compound and polyphenol-based compound.

6. A combination of a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one pesticidal compound and polyphenol-based compound.

7. A combination of a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide and polyphenol-based compound.

8. A combination of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one or derivatives thereof and polyphenol-based compound.

9. A combination of polyphenol-based compound and 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, and one or more additional different fungicides, such as, triazole fungicide, strobilurin fungicide, SDHI fungicide.

10. A combination of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, triazole fungicide and polyphenol-based compound and optionally, additional pesticidal compounds wherein, the polyphenol-based compound(s) contains at least one polyphenol.

11. A combination of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, strobilurin fungicide, polyphenol-based compound and optionally, additional pesticidal compounds.

12. A combination of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, polyphenol-based compound and succinate dehydrogenase inhibitor (SDHI) fungicide, and optionally, additional pesticidal compounds.

13. A combination of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, polyphenol-based compound and one additional fungicide.

14. A combination of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, polyphenol-based compound and two additional fungicides.

15. A combination of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, polyphenol-based compound, and one or more different pesticides fungicide.

16. The polyphenol-based compound of any one of claims 1-15 wherein the polyphenol-based compound comprises, a) naturally sourced or derived polyphenol-based compounds, and/or b) one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; and/or c) one or more of, extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or d) one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol.

17. The combination of any one of claims 5 – 15 wherein the polyphenol-based compound comprises any, some or all of: a) One or more naturally sourced or derived polyphenol-based compounds, and/or b) one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; and/or c) one or more of, extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or d) one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol.

18. A method for reducing the environmental impact of fungicidal treatment by reducing the amount of additional pesticides used as efficacy or performance enhancing agent in a combination of additional pesticide and a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one pesticide such as a fungicide, wherein the method comprises combining at least one, polyphenol-based compound with the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide and additional pesticide, wherein, i. the polyphenol-based compound comprises naturally sourced or derived polyphenol-based compounds, and/or ii. the polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or iii. the polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol, wherein the pesticidal performance of the reduced amount of additional pesticide in combination with a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one pesticide such as a fungicide and polyphenol-based compound, is equivalent or greater than the performance of a combination of unreduced amount of the same additional pesticide and the same 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one pesticide such as a fungicide, absent the polyphenol-based compound.

19. The method of claim 18, wherein the additional pesticides used as efficacy or performance enhancing agent is one or more additional fungicides.

20. A method for reducing any unwanted effect of enhancing the performance of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, with additional pesticidal compounds as performance enhancement agent wherein the method comprises combining at least one, polyphenol-based compound with the 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one and additional pesticidal performance enhancement agent thus enabling reducing the amount of pesticidal performance enhancement agent required for fungicide performance enhancement, wherein, i. the polyphenol-based compound comprises naturally sourced or derived polyphenol-based compounds, and/or ii. the polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or iii. the polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol, wherein the pesticidal performance of the reduced amount of pesticidal performance enhancement agent in combination with 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one and polyphenol-based compound, is equivalent or greater than the combination of unreduced amount of the same performance enhancing agent and 5- fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one absent the polyphenol-based compound.

21. A method for reducing any unwanted effect of fungicidal treatment by reducing the amount of fungicidal compounds used as performance enhancement agent in a combination comprising fungicidal performance enhancement agent compound and 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide, wherein the method comprises combining at least one, polyphenol-based compound with the 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide and the fungicidal performance enhancement agent compound, wherein, i. the polyphenol-based compound comprises naturally sourced or derived polyphenol-based compounds, and/or ii. the polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or iii. the polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol, wherein the fungicidal performance of the reduced amount of fungicidal performance enhancement agent compound in combination with a 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide and polyphenol-based compound, is equivalent or greater than the efficacy of a combination of unreduced amount of the same fungicidal performance enhancement agent compound and the same 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicide absent the polyphenol-based compound.

22. A method for reducing any unwanted effect of fungicidal enhancement of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one with fungicidal efficacy enhancing agent, wherein the method comprises combining at least one, polyphenol-based compound with the 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one and fungicidal efficacy enhancing agent thus enabling reducing the amount of fungicidal efficacy enhancing agent wherein, i. the polyphenol-based compound comprises naturally sourced or derived polyphenol-based compounds, or ii. the polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, or iii. the polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol, wherein the fungicidal efficacy of the reduced amount of fungicidal efficacy enhancing agent in combination with 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one and polyphenol-based compound, is equivalent or greater than the efficacy of a combination of unreduced amount of the same fungicidal efficacy enhancing agent and 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one absent the polyphenol-based compound, wherein, the fungicidal efficacy enhancing agent is selected from the group of, selected from QiI fungicide, strobilurin fungicide, succinate dehydrogenase inhibitor (SDHI) fungicide, or triazole fungicide. 24) A multi-component combination comprising at least two components: as component (1), polyphenol-based compound; and as component (2) fungicide compound selected from 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one pesticides such as, fungicides. 25) A multi-component combination comprising at least two components, as component (1), polyphenol-based compound; and as component (2) fungicide compound selected from 5-fluoro-4-imino-3-(alkyl or substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(lH)-one fungicides, the combination further comprising systemic fungicide selected from QiI fungicide; strobilurin fungicide; succinate dehydrogenase inhibitor (SDHI) fungicide; triazole fungicide. 26) The multi-component combination of any one of claims 24 - 25 wherein, i. the polyphenol-based compound comprises naturally sourced or derived polyphenol-based compounds, or ii. the polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, or iii. the polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol. 27) The multi-component combination of any one of claims 24 - 26 wherein component (1), polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins and/or proanthocyanidins. 28) The multi-component combination of any one of claims 24 - 26 wherein component (1), polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol. 29) The combination of any one of claims 5-15 comprising a composition further containing one or more agriculturally acceptable inert additives such as, thickening agent, sticking agent, surfactant, anti-oxidation agent, anti-foaming agents, thickeners, and adjuvants. 39) A kit comprising a packaged combination of a composition of polyphenol-compound and a composition of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one fungicide. 40) A composition of polyphenol-compound and a composition of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one fungicide, combined and diluted in a Tank-mix, optionally comprising, solvent, carrier or adjuvant such as, methyl soyate, spreading agents, penetrants, compatibility agents, and/or drift retardants. 41) The multi-component combination of any one of the preceding claims wherein component (1) comprises a composition of polyphenol-compound, and component (2) comprises a composition of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one fungicide, combined with an agriculturally acceptable adjuvant such as methyl soyate, and diluted in a Tank-mix. 42) A kit for obtaining the combination of any one of the preceding claims comprising a packaged composition of polyphenol-compound and packaged composition of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one fungicide wherein the combination is obtained by combining the composition of polyphenol-compound and the composition of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one. 43) A kit for obtaining the combination of any one of the preceding claims comprising a packaged composition of polyphenol-compound, a packaged composition of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one fungicide and an agriculturally acceptable adjuvant such as methyl soyate, spreading agent, penetrant, compatibility agent, or drift retardant, wherein combination is obtained by combining the composition of polyphenol-compound, the composition of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, and agriculturally acceptable adjuvant in water. 43) A method of increasing the fungicidal performance of a composition comprising 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, said method comprising adding at least one polyphenol-based compound to the composition comprising 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one wherein, i. the polyphenol-based compound comprises naturally sourced or derived polyphenol-based compounds, and/or ii. the polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or iii. the polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol. 44) A method of increasing the yield from crop plants associated with fungicidal treatment with a composition comprising a combination of 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one, said method comprising adding at least one polyphenol-based compound to the composition comprising 5-fluoro-3,4-dihydro-4-imino-3-methyl-1-tosylpyrimidin-2(1H)-one wherein, i. the polyphenol-based compound comprises naturally sourced or derived polyphenol-based compounds, and/or ii. the polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or iii. the polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol . 45) The combination, composition or method of any one of the preceding claims wherein the content of polyphenol-based compound is selected from the group of, between about 10g/ha and about 350g/ha; between about 40 g/ha and about 90 g/ha; and between 43.75g/ha and 87.5 g/ha. 46) The combination of any one of the preceding claims or compositions in which it is contained, wherein the content of polyphenol-based compound is between greater than 0% and less than 10% by weight of the combination or of the composition in which it is contained. 47) The combination of any one of the preceding claims or compositions in which it is contained, wherein the polyphenol-based component is provided as a solid or as a liquid comprising any of 7.5%, 10%, 12.5%, 15%, 17.5%, 20%, 22.5%, 25%, 27.5%, 30%, 32.5%, 35%, 37.5%, 40%, 42.5% or 45%, wherein, i. the polyphenol-based compound comprises naturally sourced or derived polyphenol-based compounds, and/or ii. the polyphenol-based compound comprises one or more of, phenolic acids; stilbenes; lignans; hydrolyzable tannins; tannic acid; flavonoids; castalagin; extracts of water-soluble tannins; extracts of water-soluble proanthocyanidins; combined extracts of natural water-soluble tannins and/or proanthocyanidins, derivatives of extracts of natural water-soluble tannins, proanthocyanidins, and/or iii. the polyphenol-based compound comprises one or more of, Cyanidin-3-O-glucoside, Sesamolin, Bisdemethoxycurcumin, Curcumin, Demethoxy curcumin, 6-Gingerol, 2-Methoxy-5-prop-1-enylphenol, Acetyl eugenol, Anethole, Estragole, Eugenol, Carnosic acid, Carnosol, Carvacrol, Epirosmanol, Rosmadial, Rosmanol, Thymol, Tannic acid, and Resveratrol. 48) The invention of products, combinations, processes, compositions, methods, system, kit or use, characterized by one or more elements disclosed in the application.