Pesticide Adjuvants

Abstract

A novel pesticide formulation comprising an adjuvant selected from diketopiperazines and a pesticide active substance. A concentrate suitable for forming the formulation is also provided. The diketopiperazine provides the adjuvant activity in the concentrate and the pesticide formulation. A method for making the formulation is also provided, as well as the use of the diketopiperazine as an adjuvant in a pesticide formulation. A method for forming the diketopiperazine is also described. The diketopiperazine can be used in formulations or seed coatings for treating plants to control pests.

Description

[Technical field]

[0001] The present invention relates generally to adjuvants for pesticide active formulations and methods of providing adjuvant activity in pesticide formulations that include said adjuvants in combination with one or more pesticide active substances. The present invention also includes treating crops with said formulations. [Background technology]

[0002] Adjuvants are generally defined as chemicals or mixtures of chemicals that can improve the biological activity or efficacy of pesticide actives. Adjuvants themselves do not control or kill pests. Instead, these additives may interact with molecular targets (e.g., cell walls, ion channels, structural proteins, enzymes, etc.) within the target organism or modify some properties (e.g., spreading, retention, penetration, droplet size) of the pesticide formulation, thereby improving the biological activity of the pesticide active on the organism. Typical types of compounds used as adjuvants may include small molecules, surfactants, emulsifiers, oils, and salts. Adjuvants typically do not inhibit the movement of the active in the treated plant. In addition, adjuvants should not cause undesirable phytotoxic effects on the plant.

[0003] Fungi are widespread in global environments and pose a major challenge to agricultural productivity. Unchecked fungal infections can result in pre- and post-harvest crop losses that can exceed 80%. To help reduce such losses and meet the growing demand for food, the use of fungicides to control fungal agricultural pests has been and will continue to be an important component of agricultural pest management systems.

[0004] There is a need to develop new strategies to deal with agricultural pests, especially fungal pests.One strategy is to develop safe and non-toxic chemical adjuvants that improve the effectiveness of existing fungicides that are already approved for use on field and greenhouse crops to prevent or reduce the impact of fungal pests on agricultural productivity.These adjuvants can improve the control of pests in the field or after harvest, thereby increasing productivity.Adjuvants can also reduce the amount of fungicide required to achieve a desired level of pest control, thus contributing to the goal of achieving sustainable productivity increases. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to provide the use of compounds in pesticide formulations in combination with pesticide active substances, which compounds may provide desired adjuvant activity, including improved efficacy of the active substance.The present invention also aims to provide the use of pesticide concentrates, dilute formulations and seed coatings containing said adjuvants.

[0006] The present invention also aims to provide compounds in agrochemical formulations, which may provide similar or improved adjuvant activity properties compared to existing adjuvants.

[0007] The present invention also aims to provide the use of compounds as adjuvants and formulations containing said compounds for use in providing adjuvant activity in pesticide formulations. [Means for solving the problem]

[0008] According to a first aspect of the present invention, there is provided an agrochemical formulation comprising: i) Formula (I) [ka] (In the formula, R 1 represents hydrogen or C1-C4 alkyl; R 2is hydrogen, C1-C4 alkyl or -CH(R 3 )(R 4 ) ; R 3 and R 4 each independently represents hydrogen, C1-C3 alkyl, phenyl, or substituted phenyl; R 5 represents hydrogen, C1-C4 alkyl, hydroxyl, methoxy or ethoxy; R 6 and R 7 each independently represents hydrogen, C1-C4 alkyl, hydroxyl, methoxy, ethoxy, or R 6 and R 7 represents a straight-chain C3 or C4 linking group which together with the N and C atoms to which they are respectively attached form a 5- or 6-membered, optionally substituted, saturated or unsaturated ring. an auxiliary selected from the diketopiperazines according to ii) at least one pesticide active substance, nutrient or biostimulant A pesticide formulation comprising:

[0009] According to a second aspect of the present invention, there is provided a concentrated formulation suitable for making an agrochemical formulation of the first aspect, comprising: i) Formula (I) [ka] (In the formula, R 1 represents hydrogen or C1-C4 alkyl; R 2 is hydrogen, C1-C4 alkyl or -CH(R 3 )(R 4 ) ; R 3 and R 4 each independently represents hydrogen, C1-C3 alkyl, phenyl, or substituted phenyl; R 5 represents hydrogen, C1-C4 alkyl, hydroxyl, methoxy or ethoxy; R 6 and R 7each independently represents hydrogen, C1-C4 alkyl, hydroxyl, methoxy, ethoxy, or R 6 and R 7 represents a linear C3-C4 linking group which together with the N and C atoms to which they are respectively attached form a 5- or 6-membered, optionally substituted, saturated or unsaturated ring) an auxiliary selected from the diketopiperazines according to ii) at least one pesticide active substance, nutrient or biostimulant A concentrated formulation comprising:

[0010] According to a third aspect of the present invention, there is provided a compound of formula (I) [ka] (In the formula, R 1 represents hydrogen or C1-C4 alkyl; R 2 is hydrogen, C1-C4 alkyl or -CH(R 3 )(R 4 ) ; R 3 and R 4 each independently represents hydrogen, C1-C3 alkyl, phenyl, or substituted phenyl; R 5 represents hydrogen, C1-C4 alkyl, hydroxyl, methoxy or ethoxy; R 6 and R 7 each independently represents hydrogen, C1-C4 alkyl, hydroxyl, methoxy, ethoxy, or R 6 and R 7 represents a linear C3-C4 linking group which together with the N and C atoms to which they are respectively attached form a 5- or 6-membered, optionally substituted, saturated or unsaturated ring) The present invention provides the use of a compound selected from the diketopiperazines according to the present invention as an adjuvant in an agrochemical formulation containing at least one agrochemical active substance, nutrient or biostimulant.

[0011] According to a fourth aspect of the present invention there is provided a method of treating a plant to control a pest comprising applying a formulation of the first aspect or a diluted concentrated formulation of the second aspect either to the plant or to the environment surrounding the plant.

[0012] According to a fifth aspect of the present invention there is provided a seed coating composition comprising an adjuvant according to the first aspect. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The compounds defined herein have been found to provide desirable co-activity properties when used in pesticide formulations with at least one pesticidal active, nutrient or biostimulant. The identified class of diketopiperazine compounds does not exhibit inherent pesticidal activity.

[0014] As used herein, the terms "for example," "for instance," "such as," or "including" are meant to introduce examples that further clarify the general subject matter. Unless otherwise specified, these examples are provided merely as an aid in understanding the application set forth in this disclosure and are not meant to be limiting in any way.

[0015] When describing the number of carbon atoms in a substituent (e.g., "C1-C4 alkyl"), it will be understood that the number refers to the total number of carbon atoms present in the substituent, including any carbon atoms present in any branched groups. Additionally, when describing the number of carbon atoms in, for example, a fatty acid, this refers to the total number of carbon atoms, including the carbon atoms of the carboxylic acid and any carbon atoms present in any branched groups.

[0016] Diketopiperazines (DKPs) are organic amide compounds that contain two amide bonds.

[0017] The adjuvant of the present invention has the formula (I) [ka] (In the formula, R 1 represents hydrogen or C1-C4 alkyl; R 2 is hydrogen, C1-C4 alkyl or -CH(R 3 )(R 4 ) ; R 3 and R 4 each independently represents hydrogen, C1-C3 alkyl, phenyl, or substituted phenyl; R 5 represents hydrogen, C1-C4 alkyl, hydroxyl, methoxy or ethoxy; and R 6 and R 7 each independently represents hydrogen, C1-C4 alkyl, hydroxyl, methoxy, ethoxy, or R 6 and R 7 represents a linear C3-C4 linking group which together with the N and C atoms to which they are respectively attached form a 5- or 6-membered, optionally substituted, saturated or unsaturated ring) The diketopiperazine is selected from the group consisting of diketopiperazines having the structure:

[0018] The term "C1-C4 alkyl" as used herein, unless otherwise defined, refers to a saturated hydrocarbon radical, straight or branched, containing from 1 to 4 carbon atoms. When any of R represents C1-C4 alkyl, said alkyl may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or the like. Preferably, it is methyl or ethyl. More preferably, it is methyl.

[0019] The term "C1-C3 alkyl" as used herein, unless otherwise defined, refers to a saturated hydrocarbon radical, straight or branched, containing 1 to 3 carbon atoms. When any of R represents C1-C3 alkyl, said alkyl may be independently selected from methyl, ethyl, n-propyl, isopropyl or the like. Preferably, it is methyl or ethyl. More preferably, it is methyl.

[0020] The term "hydroxyl," as used herein, unless otherwise stated, refers to a hydroxyl group that contains one oxygen and one hydrogen atom having the structure --OH and is bonded to an adjacent radical through the oxygen.

[0021] The terms "methoxy" and "ethoxy," as used herein, unless otherwise defined, refer to a methyl group and an ethyl group linked to an oxygen to form an alkoxy radical having the structures -O-CH3 and -O-CH2CH3, respectively, and which bond to the adjacent radical through the oxygen.

[0022] The term "phenyl," as used herein, unless otherwise defined, refers to a C6H5 organic radical derived from the benzene aromatic hydrocarbon by the removal of one hydrogen.

[0023] The term "substituted phenyl," as used herein, unless otherwise defined, refers to phenyl substituted with methyl, ethyl, methoxy, ethoxy, or halo. The substitution may be at any position on the aromatic ring, with the ortho or para positions being preferred.

[0024] The term "halo" as used herein, unless otherwise defined, refers to a halide radical derived from an element in Group VII (Group 17) of the Periodic Table. The halide radical may be independently selected from fluoro, chloro, bromo, or iodo. Preferably, it is chloro.

[0025] Preferably, R 1 represents hydrogen, methyl or ethyl, more preferably hydrogen or methyl.

[0026] Preferably, R 2 is hydrogen or -CH(R 3 )(R 4 )

[0027] R 2 -CH(R 3 )(R 4), preferably R 3 and R 4 each independently represents hydrogen, methyl, phenyl or substituted phenyl, the substituent being methyl, ethyl, methoxy or ethoxy, more preferably hydrogen or phenyl.

[0028] Preferably, R 3 and R 4 At least one of R represents phenyl while the others represent hydrogen, methyl or ethyl. More preferably, R 3 and R 4 One of R represents phenyl and the other represents hydrogen or methyl. Most preferably, R 3 and R 4 One of these represents phenyl and the other represents hydrogen.

[0029] Preferably, R 5 represents hydrogen or methyl, more preferably hydrogen.

[0030] R 6 and R 7 are each independently hydrogen, C1-C4 alkyl, hydroxyl, methoxy or ethoxy. Preferably, hydrogen or C1-C4 alkyl. More preferably, hydrogen or methyl. Even more preferably, hydrogen. Particularly preferably, R 6 and R 7 are hydrogen or R 6 is methyl, R 7 is hydrogen.

[0031] In an alternative embodiment, R 6 and R 7 R together form a single group and represent a linear C3-C4 linking group. 6 and R 7 Together with the adjacent N and C atoms to which it is attached, it forms a 5- or 6-membered optionally substituted ring, which may be a saturated or unsaturated ring.

[0032] The linear C3-C4 linking group may be selected from alkyl or alkenyl, preferably n-propyl, n-butyl, n-propenyl or n-butenyl, preferably n-propyl, n-butyl or n-propenyl.

[0033] The 5- or 6-membered ring formed in said embodiment may therefore be selected from pyrrolidine, piperidine, pyrroline, pyrrole or pyridine, preferably pyrrolidine, piperidine or pyrroline.

[0034] The 5- or 6-membered ring is optionally substituted, a term used herein meaning that the ring may be substituted or unsubstituted. The 5- or 6-membered ring may therefore include one or more substituents on the carbon backbone, said substituents independently representing C1-C4 alkyl, hydroxyl, methoxy or ethoxy. The said substituents are as defined herein.

[0035] The compounds of formula (I) may have optical isomerism around the 2-carbon of the pyrrolidine ring. It will be understood that both R and S isomers are included in the definition of the diketopiperazine of formula (I). In particular, the S isomer may be preferred.

[0036] In particular, diketopiperazines selected from the following may be preferred: [ka] [ka] [ka]

[0037] While not wishing to be bound by any particular methodology, the diketopiperazines can be formed by synthetic techniques.

[0038] Diketopiperazines and their derivatives can be produced through chemical synthesis by one of ordinary skill in the art of organic chemistry using commercially available materials and synthetic methodologies described in the scientific literature.

[0039] One such method is a two-step synthesis beginning with an amide coupling reaction between phenylpropiolic acid and L-prolinamide using a carbodiimide or phosphonium-based coupling reagent. Subsequent intramolecular cyclization through a nucleophilic α-addition catalyzed by triphenylphosphine leads to the desired diketopiperazine of formula (I). The third step can then be carried out by methylation of the amide using iodomethane in the presence of base, where a methylated variant is desired, such as (Ic) or (Id).

[0040] The supplements of the present invention may also be formed by microorganisms using fermentation-based processes.

[0041] It is understood that the properties of the adjuvant itself provide the same advantageous benefits to the agrochemical formulation containing said adjuvant, and thus, when containing the adjuvant of the present invention, an agrochemical formulation is provided that has the advantage of the properties of the adjuvant itself.

[0042] Agrochemically active compounds, including insecticides and fungicides, require formulations that allow the active compound to be absorbed by the plant / target organism.

[0043] The term "pesticidal formulation" as used herein refers to a composition containing an active pesticide and is intended to include all forms of composition, including concentrates and spray formulations. Unless otherwise stated, the pesticide formulation of the present invention may be in the form of a concentrate, a diluted concentrate or a sprayable formulation.

[0044] The adjuvants of the present invention can be combined with other components to form pesticide formulations containing at least one pesticide active.

[0045] Thus, the pesticidally active compound may be formulated as an emulsifiable concentrate (EC), an emulsion concentrate (EW), a suspension concentrate (SC), a soluble liquid (SL), as an oil-based suspension concentrate (OD) and / or as a suspoemulsion (SE).

[0046] In EC and SL formulations the active compound may be present in dissolved form, whereas in OD, SC, EW or SE formulations the active compound may be present as a solid or an emulsified liquid.

[0047] It is contemplated that the adjuvants of the present invention will find particular use in EC, EW, SC, SL, OD or SE formulations.

[0048] Agrochemical concentrates are agrochemical compositions, which may be water-soluble or water-insoluble, that are designed to be diluted with water (or a water-based liquid) to form the corresponding spray formulation. Such compositions include those in liquid form (such as solutions, emulsions or dispersions) and in solid form (especially water-dispersible solid forms) such as granules or powders.

[0049] A spray formulation is a water-soluble pesticide formulation that contains all the components desired to be applied to a plant or its environment. A spray formulation can be made by a simple dilution of a concentrate containing the desired components (except water), or by mixing the individual components, or by a combination of diluting a concentrate and adding additional individual components or mixtures of components. Typically, such final use mixing is performed in the tank where the formulation is sprayed or alternatively in a temporary holding tank for filling the spray tank. Such mixing and mixing are typically referred to as tank mixes and tank mixes.

[0050] The adjuvant can therefore be incorporated into the formulation of the agrochemical active compound (can / all-in-one formulation) or can be added after dilution of the concentrated formulation of the spray liquid (tank mix).To avoid metering errors and improve the safety of the user during the application of the agrochemical product, it is advantageous to incorporate the adjuvant into the formulation.This also avoids the unnecessary use of additional packaging materials for tank mix products.

[0051] Depending on the customer's needs, the concentrate thus formed may typically contain up to 95% by weight of pesticidal active material. The concentrate may be diluted for use to provide a diluted composition having a pesticidal activity concentration of about 0.5% to about 1% by weight. The diluted composition (e.g., for spray application rates of 10 to 500 l.ha) may be used in a range of applications. -1 In spray formulations, which may be spray formulations, the pesticidal activity concentration may range from about 0.001% to about 1% by weight of the total formulation sprayed.

[0052] The adjuvants of the present invention are typically used in an amount proportional to the amount of active pesticide in the formulation. In pesticide formulation concentrates, the proportion of adjuvant will depend on the solubility of the components in the liquid carrier. Typically, the concentration of adjuvant in such concentrates is 1% to 99% by weight. Preferably, it is 1% to 70% by weight. More preferably, it is 3% to 50% by weight.

[0053] For example, upon dilution to form a spray formulation, the adjuvant is typically present in a concentration of from 0.01% to 2% by weight of the spray formulation, more usually from 0.03% to 0.5% by weight, and more preferably from 0.12% to 0.4% by weight of the spray formulation.

[0054] The ratio of adjuvant to active pesticide in the pesticide formulation is preferably about 1:40 to about 1:1. More preferably, it is about 1:20 to about 1:1. Even more preferably, it is about 1:5 to about 1:1. This ratio range is generally maintained for concentrated forms of the formulation (e.g., where the adjuvant is included in a dispersible liquid concentrate or dispersible solid granule formulation) and in spray formulations.

[0055] When a concentrate (solid or liquid) is used as a source of active pesticide and / or adjuvant, the concentrate is typically diluted to form a spray formulation. The dilution can be with 1 to 10,000, particularly 10 to 1,000 times the total weight of the concentrate with water to form a spray formulation.

[0056] When the pesticide active is present in the water-soluble final use formulation as a solid particle, most usually the pesticide active is present as a particle that is primarily the active pesticide. However, if desired, the active pesticide can be supported on a solid carrier, such as silica or diatomaceous earth, which can be a solid support, filler or diluent material as mentioned above.

[0057] Spray formulations will typically have a pH in the range of moderately acidic (e.g., about 3) to moderately alkaline (e.g., about 10) and especially near neutral (e.g., about 5 to 8). More concentrated formulations will have similar acidity / alkalinity, but because they are mostly water-insoluble, pH is not necessarily a good criterion for this.

[0058] The agrochemical formulation may include a solvent (other than water) such as oil, which may be a vegetable oil or a mineral oil, such as monopropylene glycol, spray oil (oil included in the spray formulation as a non-surfactant adjuvant), associated with the adjuvant. Such a solvent may be included as a solvent and / or humectant for the adjuvant, for example propylene glycol, among others. When used, such a solvent is typically included in an amount of 5% to 500% by weight, desirably 10% to 100% by weight, relative to the weight of the adjuvant. Such a combination may also include salts such as ammonium chloride and / or sodium benzoate and / or urea, among others, as an aid in gel inhibition.

[0059] In an alternative embodiment, the adjuvant of the present invention may be included in a seed coating composition suitable for application to seeds. Preferably, the adjuvant of the present invention may be included in a seed coating composition.

[0060] The adjuvant is suitably present in the seed coating composition at a concentration in the range of 0.5 to 25% by weight, preferably 2 to 18% by weight, more preferably 5 to 15% by weight, especially 8 to 12% by weight, based on the total weight of the composition.

[0061] Coating may include film coating, pelleting and skinning or a combination of these techniques as known in the art. It is envisaged that the present invention applies to all of the above coating types, preferably film coating.

[0062] The seed coating composition of the present invention may be applied to the seeds in a conventional manner.

[0063] The seeds may be primed or unprimed (subjected to a treatment to improve germination rate, e.g. osmopriming, hydropriming, matrix priming).

[0064] In one embodiment, before applying the seed coating composition of the present invention, the seed is not provided with an artificial layer, for example a primer layer that includes a binder such as a polymer.Thus, the seed coating composition is preferably applied directly to the natural outer surface of the seed.Nevertheless, the seed surface can be subjected to a surface treatment before applying the seed coating composition.

[0065] Preferably, the seed coating composition is applied as a liquid composition, and / or an emulsion, and / or a dispersion, and / or a latex composition, which is then solidified (including hardened and / or dried) to form the seed coating. The term "liquid coating composition" as used in this application is meant to include coating compositions in the form of a suspension, emulsion and / or dispersion, preferably a dispersion.

[0066] Conventional means of coating can be used to coat the seeds. A variety of coating machines are available to those skilled in the art. Some well-known techniques include the use of drum coaters, fluidized bed techniques, rotary coaters (with and without integrated drying) and spouted beds. Suitably, the seed coating composition is applied to the seeds by a rotary coater, a rotary dry coater, a pan coater or a continuous treatment device.

[0067] The seed coating composition may be applied by, for example, film coating, spraying, dipping or brushing the seed coating composition. Preferably, the method includes applying the seed coating composition to form a film or seed coating layer.

[0068] Seed coating typically involves forming a securely adherent, moisture-permeable coating on the surface of a seed. The process typically involves applying a liquid seed coating composition to the seed prior to planting.

[0069] Additional film coat layers may optionally be applied over the coating layer of the present invention to provide additional benefits including, but not limited to, cosmetic, coverage, actives, nutrients and processing improvements such as faster drying, seed flowability, durability and the like.

[0070] The pesticide formulation or seed coating composition may optionally contain other components. These other components may be selected from those including: Binders, especially those which dissolve readily in water to give low viscosity solutions at high binder concentrations, such as polyvinylpyrrolidone; polyvinyl alcohol; carboxymethylcellulose; gum arabic; sugars, such as sucrose or sorbitol; starch; ethylene vinyl acetate copolymers, sucrose and alginic acid, diluents, absorbents or carriers, such as carbon black; talc; diatomaceous earth; kaolin; aluminium, calcium or magnesium stearate; sodium tripolyphosphate; sodium tetraborate; sodium sulphate; sodium, aluminium and mixed sodium aluminium silicates; and sodium benzoate, Disintegrants, such as surfactants, materials which swell in water, such as carboxymethylcellulose, collodion, polyvinylpyrrolidone and microcrystalline cellulose swelling agents; salts, such as sodium or potassium acetate, sodium carbonate, bicarbonate or sesquicarbonate, ammonium sulfate and dipotassium hydrogen phosphate; Wetting agents, such as alcohol ethoxylate and alcohol ethoxylate / propoxylate wetting agents; Dispersants, such as sulfonated naphthalene formaldehyde condensates and acrylic copolymers, such as comb copolymers having polyethylene glycol side chains capped onto a polyacrylic acid backbone; emulsifiers, such as alcohol ethoxylates, ABA block copolymers or castor oil ethoxylates; a defoamer, such as a polysiloxane defoamer, typically in an amount of 0.005% to 10% by weight of the formulation; viscosity modifiers, for example commercially available water-soluble or miscible gums, such as xanthan gum and / or cellulose derivatives, such as carboxy-methyl, ethyl or propyl cellulose; and / or preservatives and / or antimicrobial substances, for example organic acids or their esters or salts, for example ascorbic acid, e.g. ascorbyl palmitate, sorbic acid, e.g. potassium sorbate, benzoic acid, e.g. benzoic acid and methyl and propyl 4-hydroxybenzoate, propionic acid, e.g. sodium propionate, phenols, e.g. sodium 2-phenylphenate; 1,2-benzisothiazolin-3-one; or formaldehyde as such or paraformaldehyde; or inorganic materials, for example sulfurous acid and its salts, typically in an amount of 0.01% to 1% by weight of the formulation.

[0071] The pesticide formulation or seed coating composition according to the invention may also contain components such as surface active materials which form part of an emulsifier system. The surface active materials may include surfactant dispersants.

[0072] Other adjuvants within the scope of the present invention, such as surfactant adjuvants, may be included in and used in the compositions and formulations of the present invention.Examples include alkyl polysaccharides (more precisely called alkyl oligosaccharides); fatty amine ethoxylates, such as coconut alkylamine 2EO; and derivatives of alkyl(en)yl succinic anhydrides, particularly those described in PCT applications WO 94 / 00508 and WO 96 / 16930.

[0073] The formulation / composition may comprise one or more biologically active ingredients (including plant promoters, in particular plant protection products (also referred to as PPPs)). Suitable examples of active ingredients, in particular plant promoters, are fungicides, bactericides, insecticides, nematicides, molluscicides, biological preparations, acaricides or miticides, repellents and biocides. Further possible active ingredients include disinfectants, microorganisms, rodenticides, herbicides (weed killers), attractants, (bird) repellents, plant growth regulators (such as gibberellic acid, auxins or cytokinins), nutrients (such as potassium nitrate, magnesium sulfate, iron chelators), plant hormones, minerals, plant extracts, germination stimulants, pheromones, biological preparations, etc.

[0074] Suitable agrochemical active substances for use in the formulation or seed coating composition according to the present invention are all agrochemically active compounds that can be solid or liquid at room temperature.It is envisaged that the adjuvant of the present invention will have broad applicability to all types of agrochemical active substances.

[0075] Agrochemical active substances in the context of the present invention refer to biocides, which are more specific chemical substances capable of killing various forms of living organisms, used in the field as plant protection agents, medicine, agriculture, forestry and mosquito control, etc. The so-called plant growth regulators are also counted in the group of biocides.

[0076] Biocides for use in the pesticide formulations or seed coating compositions of the invention are typically divided into two subgroups: Pesticides, including fungicides, herbicides, insecticides, algaecides, molluscicides, acaricides and rodenticides, and · Antimicrobial substances including bactericides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals and antiparasitics.

[0077] In particular, biocides selected from insecticides, fungicides or herbicides may be particularly preferred.

[0078] It will be understood that the term "pesticide" refers to any substance or mixture of substances intended to prevent, destroy, repel or weaken any pest.Pesticides can be chemicals or biological agents (such as viruses or bacteria) used against pests, including insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms) and pathogens, that compete with humans for food, destroy property, spread disease or are pests.The following examples show pesticides suitable for the pesticide composition according to the present invention.

[0079] Fungicides are chemical controls against fungi. Fungicides are chemical compounds used to prevent the spread of fungi in gardens and crops. Fungicides are also used to suppress fungal infections. Fungicides can be contact or systemic. Contact fungicides kill fungi when they come into contact with the fungicide carried on the leaf surface. Systemic fungicides are absorbed into plant tissue and kill the fungus when it attempts to invade the host.

[0080] Examples of fungicides suitable according to the invention include the following species: (3-ethoxypropyl)mercuric bromide, 2-methoxyethylmercuric chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate, 8-phenylmercuryoxyquinoline, acibenzolar, acyl amino acid fungicides, acipetax, aldimorph, aliphatic nitrogen fungicides, allyl alcohol, amide fungicides, ampropylphos, anilazine, anilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, azaconazole, adityram, azoxystrobin, barium polysulfide, Benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benzalkonium chloride, benzamacryl, benzamide fungicides, benzamorph, benzanilide fungicides, benzimidal fungicides, benzimidal precursor fungicides, benzimidazolyl carbamate fungicides, benzohydroxamic acid, benzothiazole fungicides, besoxazin, binapropacryl, biphenyl, bitertanol, bithionol, blasticidin-S, Bordeaux mixture, boscalid, bridged diphenyl fungicides, bromuconazole, bupiri Mate, Burgundy liquid mixture, Buthiobate, Butylamine, Calcium polysulfide, Captafol, Captan, Carbamate fungicides, Carbamorph, Carbanilate fungicides, Carbendazim, Carboxin, Carpropamid, Carvone, Cheshunt mixture, Quinomethionate, Chlobenthiazone, Chloraniformethane, Chloranil, Chlorphenazole, Chlorodinitronaphthalene, Chloroneb, Chloropicrin, Chlorothalonil, Chloroquinox, Chlozolinate, Ciclopirox, Climbazole, Clotrimazole, Conazole Fungicides, Conazole Fungicides (Imidazoles), Conazole Fungicides (Triazoles), Copper (II) Acetate, Copper (II) Carbonate, Basic Copper Fungicides, Copper Hydroxide, Copper Naphthenate, Copper Oleate, Copper Oxychloride, Copper (II) Sulfate, Copper Sulfate, Basic Copper Zinc Chromate, Cresols, Kufuraneb, Cuprobam, Cuprous Oxide, Cyazofamid, Cyclafuramide, Cycladithiocarbamate Fungicides, Cycloheximide, Cyflufenamid, Cymoxanil, Cypendazole, Cyproconazole, Cyprodinil, Dazomet, DBCP, Debacarb, Decafentin, Dehydroacetic Acid,Dicarboximide fungicides, dichlofluanid, dicloron, dichlorophen, dichlorophenyl, dicarboximide fungicides, diclozolin, diclobutrazol, diclocymet, diclomedine, dicloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, diflumetrim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinitrophenol fungicides, dinobuton, dinocap, dinokton, dinopenton, dinosulfone, dinotervone, diphenylamine, dipyrithione, disulfiram, ditalim Phos, dithianon, dithiocarbamate fungicides, DNOC, dodemorph, dodicin, dodine, donatozine, drazoxolone, edifenphos, epoxiconazole, etaconazole, ethem, ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, f Fennitropan, Fenoxanil, Fenpiclonil, Fenpropizin, Fenpropimorph, Fentin, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Flumetober, Flupicolide, Fluorimide, Fluotrimazole, Fluoxastrobin, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Formaldehyde, Fosetyl, Fuberidazole, Furalaxyl, Furametpyr, Furamid fungicide, Fluanilide fungicide, Flucarbanil, Fluconazole, Fluconazole-Cyclohexyl furfural, flumecyclox, furofanate, gliodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiophos, hydragafen, hymexazole, imazalil, imibenconazole, imidazole fungicides, iminoctadine, inorganic fungicides, inorganic mercury fungicides, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isovalerion, kasugamycin, kresoxim methyl,Lime sulfur, mancopper, mancozeb, maneb, mebenil, mecarbinzide, mepanipyrim, mepronil, mercuric chloride, mercuric oxide, mercurous chloride, mercuric fungicides, metalaxyl, metalaxyl-M, metam, metazoxolone, metconazole, methasulfocarb, metofloxam, methyl bromide, methyl isothiocyanate, methylmercuric benzoate, methylmercuric dicyandiamide, methylmercuric pentachlorophenoxide, metiram, metominostrobin, metrafenone, methsulfovax, milneb, morpholine fungicides, myclobutanil, Mycorzolin, N-(ethylmercury)-p-toluenesulfonanilide, Nabam, Natamycin, Nitrostyrene, Nitrotarisopropyl, Nuarimol, OCH, Octilinone, Ofurace, Organomercurial Fungicides, Organophosphorus Fungicides, Organotin Fungicides, Orysastrobin, Oxadixyl, Oxathiin Fungicides, Oxazole Fungicides, Oxine Copper, Oxpoconazole, Oxycarboxin, Pefurazoate, Penconazole, Pencycuron, Pentachlorophenol, Penthiopyrad, Phenylmercuricurea, Phenylmercuric Acetate, Phenylmercuric Chloride, Pyro Phenylmercuric derivatives of catechol, phenylmercuric nitrate, phenylmercuric salicylate, phenylsulfonamide fungicides, phosdifen, phthalide, phthalimide fungicides, picoxystrobin, piperalin, polycarbamates, polymeric dithiocarbamate fungicides, polyoxins, polyoxorim, polysulfide fungicides, potassium azide, potassium polysulfide, potassium thiocyanate, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazide, prothiocarb, prothioconazole, pyracarbollide, pyraclostrobin, pyrazole fungicides, pyrazophos, pyridine fungicides, pyridinitrile, pyrifenox, pyrimethanil, pyrimidine fungicides, pyroquilon, pyroxchlor, piroxiphia, pyrrole fungicides, quinacetol, quinazamide, quinconazole, quinoline fungicides, quinone fungicides, quinoxaline fungicides, quinoxyfen, quintozene, labenzazole, salicylanilide, silthiofam, simeconazole, sodium azide, sodium orthophenylphenol, sodium pentachlorophenoxide, sodium polysulfide,Spiroxamine, Streptomycin, Strobilurin Fungicides, Sulfonanilide Fungicides, Sulfur, Sultropene, TCMTB, Tebuconazole, Tecloftalam, Tecnazene, Tecolum, Tetraconazole, Thiabendazole, Thiadifluor, Thiazole Fungicides, Thithiofen, Thifluzamide, Thiocarbamate Fungicides, Thiochlorfenfim, Thiomersal, Thiophanate, Thiophanate-methyl, Thiophene Fungicides, Thioquinox, Thiram, Tiadinil, Tioximide, Thibed, Tolclofos-methyl, Tolnaftate , tolylfluanid, tolylmercuric acetate, triadimefon, triadimenol, triamiphos, triarimol, triazbutyl, triazine fungicides, triazole fungicides, triazoxide, tributyltin oxide, triclamide, tricyclazole, trifloxystrobin, triflumizole, triforine, triticonazole, unclassified fungicides, undecylenic acid, uniconazole, urea fungicides, validamycin, valinamide fungicides, vinclozolin, zaliramide, zinc naphthenate, zineb, ziram, zoxamide and mixtures thereof.

[0081] Herbicides are pesticides used to kill undesirable plants. Selective herbicides kill specific targets while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of weeds and are often based on plant hormones. Herbicides used to clear disturbed land are non-selective and kill all plant material they come into contact with. Herbicides are widely used in agriculture and in garden lawn care. They are applied in integrated vegetation management (TVC) programs for highway and railroad maintenance. Smaller amounts are used to manage forests, rangelands, and areas left as wildlife habitat.

[0082] Suitable herbicides may be selected from the group comprising: triazine herbicides such as aryloxycarboxylic acids, e.g. MCPA, allyloxyphenoxypropionic acid, e.g. clodinafop, cyclohexanedione oximes, e.g. sethoxydim, hydroxybenzonitriles, e.g. bromoxynil, sulfonylureas, e.g. nicosulfuron, triazolopyrimidines, e.g. penoxsulam, trikethiones, e.g. mesotrione, metribuzin, hexazinone or atrazine; sulfonylurea herbicides, e.g. chlorsulfuron; uracils, e.g. lenacil, bromacil or terbacil; urea herbicides, e.g. linuron, diuron, siduron or nebulon; alachlor or metolachlor; cetoanilide herbicides; thiocarbamate herbicides such as benthiocarb, triallelate; oxadiazolone herbicides such as oxadiazon; isoxazolidone herbicides, phenoxyacetic acid; diphenyl ether herbicides such as fluazifop, acifluorfen, bifenox or oxyfluorfen; dinitroaniline herbicides such as trifluralin; organophosphonic acid herbicides such as glufosinate salts and esters and glyphosate salts and esters; and / or dihalobenzonitrile herbicides such as bromoxynil or ioxynil, benzoic acid herbicides, dipyridylium herbicides such as paraquat; and other herbicides such as clomazone, carfentrazone, saflufenacil and pyroxasulfone.

[0083] Particularly preferred herbicides may be selected from 2,4-dichlorophenoxyacetic acid (2,4-D), atrazine, dicamba as a benzoic acid, glyphosate, glufosinate, imazapic as an imidazolinone, metolachlor as a chloroacetamide, picloram, clopyralid and triclopyr as a pyridine carboxylic acid or synthetic auxins, their respective water soluble salts and esters and mixtures thereof.

[0084] Insecticides are pesticides used against insects in all their forms, including ovicides and larvicides, which are used against insect eggs and larvae. Insecticides are used in agriculture, medicine, industry and the home.

[0085] Suitable insecticides may include those selected from the following: chlorinated insecticides such as camphechlor, DDT, hexachlorocyclohexane, gamma hexachlorocyclohexane, methoxychlor, pentachlorophenol, TDE, aldrin, chlordane, chlordecone, dieldrin, endosulfan, endrin, heptachlor, mirex and mixtures thereof; e.g., acephate, azinphos methyl, bensulide, chlorethoxyphos, chlorpyrifos, chlorpyrifos methyl, diazinon, dichlorvos (DDVP), dicrotophos, dimethoate, disulfon, ethoprop, fenamiphos, fenitrothion, fenthion, fosthiazate, malathion, methamidophos, methidathion, methyl parathion, mevinphos, naled, omethoate, oxydemeton methyl, parathion, folate, phosalone, phosmet, fostebupidine, fostib ... organophosphorus compounds such as rim, pirimiphos-methyl, profenofos, terbufos, tetrachlorvinphos, tribufos, trichlorfon and mixtures thereof; carbamates such as aldicarb, carbofuran, carbaryl, methomyl, 2-(l-methylpropyl)phenylmethylcarbamate and mixtures thereof; pyrethroids such as allethrin, bifenthrin, deltamethrin, permethrin, resmethrin, sumithrin, tetramethrin, tralomethrin, transfluthrin and mixtures thereof; compounds derived from plant toxins such as derris (rotenone), neem, neem (azadirachtin), nicotine, caffeine and mixtures thereof; neonicotinoids such as imidacloprid; abamectins, e.g. emamectin; oxadiazines such as indoxacarb; and / or anthranilic diamides such as rynaxypyr.

[0086] Acaricides are pesticides that kill mites. Antibiotic acaricides, carbamate acaricides, formamidine acaricides, mite growth regulators, organochlorines, permethrin and organophosphate acaricides all belong to this category. Molluscicides are pesticides used to control mollusks, such as moths, slugs and snails. These substances include metaldehyde, methiocarb and aluminium sulfate. Nematicides are a type of chemical pesticide used to kill parasitic nematodes (a phylum of insects).

[0087] Most preferably, the active substances present in the pesticide formulations or seed coating compositions of the invention are selected from triazole fungicides, strobilurin fungicides or combinations thereof, in particular tebuconazole, flutriafol, carbendazim, azoxystrobin, kresoxim-methyl, cyproconazole or pyraclostrobin.

[0088] Nutrients may be present in addition to or as an alternative to the pesticide active. In such formulations / compositions, the nutrients are typically in dry form.

[0089] The nutrients may preferably be solid-phase nutrients. Solid nutrients are understood in the present invention to mean substances with a melting point above 20° C. (at standard pressure). Solid nutrients may also include insoluble nutrients, i.e. nutrients that are so soluble in water that significant solids are present in the concentrate after addition.

[0090] Nutrients refer to chemical elements and compounds that are desired or necessary to promote or improve plant growth. Suitable nutrients are generally described as macronutrients or micronutrients. Suitable nutrients for use in the concentrate according to the present invention are all nutritional compounds.

[0091] Micronutrients typically refer to trace metals or trace elements, and are often applied in lower doses.Suitable micronutrients include trace elements selected from zinc, boron, chlorine, copper, iron, molybdenum and manganese.Micronutrients can be in soluble form or can be included as insoluble solids, and can be salts or chelated.

[0092] Macronutrients typically refer to those containing nitrogen, phosphorus and potassium, and include fertilizers and water conditioners, such as ammonium sulfate. Suitable macronutrients include fertilizers and other nitrogen-, phosphorus-, potassium-, calcium-, magnesium-, sulfur-containing compounds and water conditioners.

[0093] Suitable fertilizers include inorganic fertilizers that provide nutrients such as nitrogen, phosphorus, potassium, or sulfur. The fertilizers may be included in diluted formulations at relatively low concentrations or as more concentrated solutions, which may include solid fertilizers and solutions at much higher levels.

[0094] It is envisioned that the inclusion of nutrients will depend on the particular nutrient, with micronutrients typically being included in lower concentrations, while macronutrients will typically be included in higher concentrations.

[0095] The biostimulant component may be added to the formulation or seed coating composition to promote crop growth. The biostimulant component may include or consist of one or more biostimulants.

[0096] Examples of useful biostimulants include, but are not limited to, plant growth hormones and plant growth regulators such as cytokinins, auxins, gibberellins, ethylene, abscisic acid, etc. Other biostimulants include protein hydrolysate derivatives, seaweed extracts, amino acids, plant extracts, chitosan derivatives, biopolymers, inorganic compounds, humic substances, microbial inocula and microbial products or mixtures thereof.

[0097] The adjuvants of the present invention may find application in providing co-activity to agrochemical formulations in which they are included, and in particular in providing fungicide co-activity.

[0098] As used herein, the term "adjuvant" or "co-active" refers to a compound that, when added to an agrochemical formulation, will improve the desired agrochemical effect. The adjuvant may affect the diluent, mixture, active substance, or target by improving the performance of the active substance with the adjuvant. The adjuvant may be used to modify the epidermal layer of the leaf surface to allow the pesticide to enter and / or sensitize the target pest to the active pesticide in the agrochemical formulation, so that the pesticide adheres to the area where it acts.

[0099] Specific co-active effects may include surfactants, emulsifiers (dispersants and suspending agents), oils, emulsifiable oils, admixtures, buffers and regulators, defoamers, adhesion agents, scatter retardants, thickeners, spreading agents (wetting agents), fixatives (builders and extenders), plant penetrants, transporters, soil penetrants, stabilisers (UV filters) and / or pest sensitisers to the active pesticide.

[0100] Preferably, the adjuvants of the present invention may find use as the sole component or the primary functional agent in adjuvants formulated for use as tank add or directly in pesticide concentrates.

[0101] As a measure of adjuvant activity with respect to the activity of a fungicide alone (e.g. pyraclostrobin) against B. cinerea, one can define the value of percent inhibition (adjuvant and fungicide) divided by percent inhibition (fungicide), with higher values ​​being desirable.

[0102] A value of 1 would therefore indicate equal activity of the adjuvant / fungicide combination relative to the fungicide alone, whereas a value greater than 1 would indicate greater activity with the adjuvant / fungicide combination than the fungicide alone.

[0103] Active substances of the present invention may have a value greater than 1. Preferably, it is greater than 1.2, and most preferably, it is greater than 1.4.

[0104] All of the features described in this specification may be combined with any of the above aspects in any combination. EXAMPLES

[0105] In order that the invention may be more readily understood, reference is now made, by way of example, to the following descriptions.

[0106] It will be understood that all tests and physical properties listed are determined at atmospheric pressure and room temperature (i.e., 20-25° C.) unless otherwise stated herein or in the referenced test methods and procedures.

[0107] formation To synthesize cyclo(-Phe-Pip) diketopiperazine (If), pipecolic acid (201.7 mg, 1.5617 mmol) and phenylalanine methyl ester (3.33 g, 15.4 mmol) were dissolved in dimethylformamide (20 mL) and cooled to 0° C. in an ice bath, after which benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate (PyBOP, 1.905 g, 3.661 mmol) and triethylamine (0.5 mL, 3.587 mmol) were added. The reaction solution was allowed to warm to room temperature and stirred overnight.

[0108] The reaction was concentrated in vacuo to give the crude product, which was fractionated by normal phase chromatography (silica, hexanes→ethyl acetate) using a CombiFlash® NextGen system (Teledyne Isco). The fractions containing the dipeptide product (380.0 mg, 1.3087 mmol, 83.8% yield) were combined and evaporated in vacuo before proceeding to the next step.

[0109] The dipeptide was dissolved in methanol (75 mL) and then triethylamine (1 mL) was added. The reaction was heated to 60° C. in an oil bath for 3 days, after which the reaction was concentrated in vacuo. The reaction product was purified by normal phase chromatography (silica, hexanes→ethyl acetate) using a CombiFlash® NextGen system (Teledyne Isco). Fractions containing the cyclo(-Phe-Pip) diketopiperazine product (75.5 mg, 0.2923 mmol, 22% yield) were combined and evaporated in vacuo.

[0110] To synthesize cyclo(-Phe-dhPro) diketopiperazine (Ig), Boc-3,4-dehydro-L-proline (257.4 mg, 1.207 mmol), phenylalanine methyl ester (390.4 mg, 1.810 mmol) and N-hydroxysuccinimide (205.0 mg, 1.781 mmol) were dissolved in anhydrous CHCl (10 mL). The mixture was cooled to 0° C. in an ice bath, and then diisopropylcarbodiimide (0.273 mL, 1.763 mmol) and triethylamine (0.245 mL, 1.758 mmol) were added.

[0111] The reaction was allowed to warm to room temperature and stirred overnight, then partitioned between ethyl acetate and water. The organic phase was collected and evaporated in vacuo to give the crude product, which was fractionated by normal phase chromatography (silica, hexanes→ethyl acetate) using a CombiFlash® NextGen system (Teledyne Isco).

[0112] Fractions containing the dipeptide product (323.1 mg, 0.8629 mmol, 71% yield) were combined and evaporated in vacuo before proceeding to the next step. The dipeptide underwent Boc deprotection by dissolving the dipeptide in dichloromethane (6 mL) followed by the addition of trifluoroacetic acid (6 mL). The reaction was stirred at room temperature overnight and then the reaction was concentrated in vacuo.

[0113] The crude product was used in the next step without further purification or characterization. The deprotected dipeptide was dissolved in methanol (75 mL) and then triethylamine (1 mL) was added. The reaction was heated to 60° C. in an oil bath for 3 days, after which the reaction was concentrated in vacuo.

[0114] The reaction product was purified by normal phase chromatography (silica, hexanes → ethyl acetate) using a CombiFlash® NextGen system (Teledyne Isco). Fractions containing the cyclo(-Phe-Pip) diketopiperazine product (65.2 mg, 0.2691 mmol, 31% yield over two steps) were combined and evaporated in vacuo.

[0115] The structure of the diketopiperazine was elucidated by a combination of mass spectrometry and NMR analysis. The NMR spectra are 1 H and 13 C were recorded on a Bruker Avance III 400 MHz NMR spectrometer operating at 400 and 150 MHz. Spectra were referenced to residual solvent signals.

[0116] NMR analysis of the metabolites was consistent with literature data and confirmed the structures as diketopiperazines (Ia, Ib, Ic, Id, Ie, If, and Ig).

[0117] Auxiliary activity parameters It will be understood that the parameters "percent inhibition" and "fold change" are presented and calculated as follows:

[0118] Percent Inhibition - Percent inhibition will be understood to indicate the amount of fungicide and / or adjuvant that inhibits the visible growth of a microorganism after 48 hours incubation at 22°C compared to a vehicle treated control. This is calculated using the following formula: [(O C -O T ) / O C ]×100% Where: O C = diameter of colonies grown on agar supplemented with vehicle (i.e., vehicle-treated control), and O T = diameter of colonies grown on agar supplemented with fungicides and / or adjuvants formulated in an appropriate vehicle (i.e. solvents such as water, C2H5OH, CH3OH, CH3CN, DMSO, etc.).

[0119] Fold Change - Fold change is a measure of the adjuvant / fungicide combination in inhibiting microorganisms compared to the fungicide alone. It indicates how well the adjuvant performs compared to the fungicide alone. It is calculated using the following formula: INH AF / INH F Where: INH AF = Percentage inhibition of fungal growth when treated with fungicide and adjuvant, and INH F = percent inhibition of fungal growth when treated with fungicide only.

[0120] Results of auxiliary activity Botrytis cinerea (ATCC 90479) was cultured on Difco Potato Dextrose Agar (PDA) with a diurnal UV cycle (12 hours UV light and 12 hours dark) for 7 days. Spores were harvested in buffered sterile saline (w / v: 0.9% NaCl with 1% Tween® 80) and counted using a hemocytometer. Spore suspensions were diluted to 8.5 x 10 to produce a standardized inoculum. 6 The final concentration was adjusted to 100 spores / mL.

[0121] To prepare mycelial fragments for testing adjuvants, 8.5 x 10 4 Spores of the strain were used to inoculate 10 mL of Difco Potato Dextrose Broth in a 150×25 mm tube. The tube was incubated for 48 hours at 220 RPM and 22° C.

[0122] To generate mycelial fragments from the cultures, the cultures were transferred to 50 mL plastic conical tubes containing approximately 20 sterile 5 mm diameter glass beads and vortexed for 5 min. After vortexing, the tubes were allowed to stand for 5 min to allow large mycelial aggregates to settle, and the top layer containing the mycelial fragments was then removed and used as inoculum for the growth inhibition assay.

[0123] Fungicides and adjuvants were dissolved in methanol and added to the molten PDA (approximately 50° C.), then the agar was dispensed into the wells of a 12-well multiwell plate (1 mL / well). The plates were cooled to room temperature and 10 μL of mycelial inoculum was added to the center of each well. The plates were incubated for 48 hours at 22° C., then the colony diameters were measured using a digital caliper. Biological growth controls consisted of mycelium and vehicle (0.07% methanol) and negative controls were medium and vehicle (0.07% methanol).

[0124] The results for the co-active substances of the invention are shown in Table 1. Co-activity with pyraclostrobin against B. cinerea was observed for each of the compounds tested, most notably diketopiperazine Ie and diketopiperazine Ic, which showed a 1.56-fold and 1.52-fold increase in fungicidal activity compared to pyraclostrobin alone at 0.06 μg / mL.

[0125] Diketopiperazines (Ia, Ib, Ic, Id, Ie, If, and Ig) did not show any specific fungicidal activity by themselves at any of the concentrations tested.

[0126] [Table 1]

[0127] The effect of the adjuvant on fungicidal activity is expressed as the fold increase in growth inhibition. A value of 1 indicates no increase in fungicidal activity. Values ​​less than 1 indicate a decrease in fungicidal activity, and values ​​greater than 1 indicate an increase in fungicidal activity.

[0128] In Table 1 it can be seen that the adjuvant clearly provides adjuvant activity properties to the active agent at various active concentrations.

[0129] It will be understood that the invention is not limited to the details of the above embodiments, which are given by way of example only. Many variations are possible.

Claims

1. A pesticide formulation comprising: i) Formula (I) 【Chemistry 1】 (In the formula, R １ is hydrogen or C １ ~C ４ represents alkyl; R ２ is hydrogen, C １ ~C ４ Alkyl or -CH(R ３ ) (R ４ ) represents; R ３ and R ４ are each independently hydrogen, C １ ~C ３ represents alkyl, phenyl or substituted phenyl; R ５ is hydrogen, C １ ~C ４ represents alkyl, hydroxyl, methoxy or ethoxy; R ６ and R ７ are each independently hydrogen, C １ ~C ４ alkyl, hydroxyl, methoxy, ethoxy, or R ６ and R ７ are straight-chain C alkyl groups which together with the N and C atoms to which they are respectively attached form a 5- or 6-membered optionally substituted saturated or unsaturated ring; ３ Or C ４ represents a linking group) an adjuvant selected from diketopiperazines according to the formula: ii) at least one pesticide active substance, nutrient or biostimulant Pesticide formulations containing

2. R １ represents hydrogen, methyl or ethyl; R ２ is hydrogen or —CH(R ３ ) (R ４ ) represents; R ３ and R ４ at least one of represents phenyl while the others represent hydrogen, methyl or ethyl; R ５ represents hydrogen or methyl; R ６ and R ７ are each independently hydrogen or C １ ~C ４ represents alkyl, or R ６ and R ７ are straight-chain C alkyl groups which together with the N and C atoms to which they are respectively attached form a 5- or 6-membered optionally substituted saturated or unsaturated ring; ３ Or C ４ The formulation of claim 1 , wherein:

3. R １ represents hydrogen or methyl; R ２ is hydrogen or —CH(R ３ ) (R ４ ) represents; R ３ and R ４ at least one of represents phenyl while the others represent hydrogen or methyl; R ５ represents hydrogen; R ６ and R ７ each independently represents hydrogen or methyl, or R ６ and R ７ are together a linear C selected from n-propyl, n-butyl, or n-propenyl ３ Or C ４ 3. The formulation of claim 1 or 2, wherein:

4. The adjuvant has the following formula: 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 3. The formulation according to claim 1 or 2, wherein the diketopiperazine is selected from the group consisting of:

5. A concentrated formulation suitable for making the pesticide formulation of claim 1 or 2, i) Formula (I) 【Transformation 5】 (In the formula, R １ is hydrogen or C １ ~C ４ represents alkyl; R ２ is hydrogen, C １ ~C ４ Alkyl or -CH(R ３ ) (R ４ ) represents; R ３ and R ４ are each independently hydrogen, C １ ~C ３ represents alkyl, phenyl or substituted phenyl; R ５ is hydrogen, C １ ~C ４ represents alkyl, hydroxyl, methoxy or ethoxy; R ６ and R ７ are each independently hydrogen, C １ ~C ４ alkyl, hydroxyl, methoxy, ethoxy, or R ６ and R ７ are straight-chain C alkyl groups which together with the N and C atoms to which they are respectively attached form a 5- or 6-membered optionally substituted saturated or unsaturated ring; ３ ~C ４ represents a linking group) an adjuvant selected from diketopiperazines according to the formula: ii) at least one pesticide active substance, nutrient or biostimulant A concentrated formulation comprising:

6. 6. The concentrated formulation of claim 5, which is an emulsifiable concentrate (EC), emulsion concentrate (EW), suspension concentrate (SC), soluble liquid (SL), oil-based suspension concentrate (OD) or suspoemulsion (SE).

7. Formula (I) 【Transformation 6】 (In the formula, R １ is hydrogen or C １ ~C ４ represents alkyl; R ２ is hydrogen, C １ ~C ４ Alkyl or -CH(R ３ ) (R ４ ) represents; R ３ and R ４ are each independently hydrogen, C １ ~C ３ represents alkyl, phenyl or substituted phenyl; R ５ is hydrogen, C １ ~C ４ represents alkyl, hydroxyl, methoxy or ethoxy; R ６ and R ７ are each independently hydrogen, C １ ~C ４ alkyl, hydroxyl, methoxy, ethoxy, or R ６ and R ７ are straight-chain C alkyl groups which together with the N and C atoms to which they are respectively attached form a 5- or 6-membered optionally substituted saturated or unsaturated ring; ３ ~C ４ represents a linking group) 10. Use of a compound selected from the group consisting of diketopiperazines according to claim 1 as an adjuvant in an agrochemical formulation comprising at least one agrochemical active substance, nutrient or biostimulant.

8. 10. A method of treating plants to control pests, comprising applying a formulation according to claim 1 or 2 to either the plant or the environment surrounding the plant.

9. A seed coating composition comprising the diketopiperazine adjuvant of claim 1 or 2.

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