COMPOSITIONS OF DICARBOXYLIC ACID DERIVATIVES.
Patent Information
- Application Number
- MX2021014776
- Authority / Receiving Office
- MX · MX
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2019-06-05
- Filing Date
- 2021-12-01
- Publication Date
- 2026-02-25
- Estimated Expiration
- 2040-06-04
AI Technical Summary
Existing dicarboxylic acid hydrazide compositions degrade over time, releasing hydrazine as an impurity, which increases toxicity and reduces potency, and current methods to stabilize these compositions lead to crystallization and instability.
Incorporating transition metal ions or their salts into dicarboxylic acid hydrazide compositions to control and reduce hydrazine levels below 1 ppm, maintaining stability and reducing toxicity.
The compositions remain stable with hydrazine levels below 1 ppm for up to 2 years, ensuring safety and effectiveness in agricultural and industrial applications.
Abstract
Description
COMPOSITIONS OF DICARBOXYLIC ACID DERIVATIVES TECHNICAL FIELD The present invention relates to a composition of dicarboxylic acid hydrazides. The present invention also relates to a process for preparing the composition of dicarboxylic acid hydrazides. BACKGROUND Hydrazides have a wide range of applications, including as pharmaceuticals, plant preservatives, in the manufacture of polymers, adhesives, and for many other industrial and other purposes. Maleic hydrazide (MH) is a well-known synthetic compound that regulates plant growth. It is used as a foliar treatment on potatoes to prevent sprouting and weed growth during storage. It is also used to control onion sprouting, tobacco suckers, and the growth of weeds, grasses, and trees in and around meadows, lawns, ornamental plants, non-carrying citrus groves, utility and road rights-of-way, airports, and industrial soils. Hydrazine is a raw material used to manufacture maleic hydrazide and is considered a toxic impurity in the final product, with very low permissible levels. Hydrazine is a highly toxic and dangerously unstable compound known for its carcinogenic properties. Maleic hydrazide degrades over time and releases free hydrazine during storage. Over time, hydrazine levels are observed to increase in the product. Several methods used in the formulation of maleic hydrazide, such as neutralization with potassium salts, drying steps during granule preparation, and the addition of chelating agents to liquid maleic hydrazide compositions, tend to increase the levels of free hydrazine in the product. In such cases, adhering to the prescribed specification is challenging, even if the raw materials used meet the prescribed specifications. Measures employed to correct this anomaly have resulted in less stable compositions, with problems such as crystallization in the liquid composition plaguing manufacturers. Therefore, considering these challenges, there is an urgent need for a composition that remains stable over a significant period. The present inventors address this need and provide a composition of dicarboxylic acid hydrazides. Therefore, the objective of the present invention is to provide a composition of dicarboxylic acid hydrazides that is stable during storage. SUMMARY OF THE INVENTION In accordance with the foregoing objective, the present invention provides a composition comprising: a. at least one compound selected from a dicarboxylic acid hydrazide and b. at least one ion of a transition metal or a salt thereof. In another aspect, the present invention provides a substantially hydrazine-free composition having hydrazine levels below 1 ppm. In another aspect, the present invention provides a method for preparing a composition with low toxicity. In another aspect, the present invention provides for the use of transition metal ions to control or reduce the levels of free hydrazine in compositions comprising at least one compound selected from the dicarboxylic acid hydrazides. In another aspect, the present invention provides a method for treating a plant in a location by applying a composition comprising: a. at least one compound selected from a dicarboxylic acid hydrazide; and b. at least one transition metal ion or salt thereof. DETAILED DESCRIPTION Dicarboxylic acid hydrazides are commonly used in agriculture as plant growth regulators, foliar applications, bud retardants, and for similar purposes. They also have applications in the resin industry as hardeners, crosslinkers, etc. Over a period of time during storage, hydrazides degrade to release hydrazine, which contributes as an impurity in the final product. As a result, it contributes to potential toxicity and harm to consumers, as well as a decrease in the product's potency for its intended action, leading to reduced profitability. Certain preparation processes of the formulation also contribute to a significant increase in hydrazine levels in the final product, causing it to fall outside the prescribed specification. Surprisingly, the inventors of the present invention found that adding transition metal ions or a salt thereof to the composition reduces the amount of hydrazine present. Therefore, the inventors of the present invention were able to provide a dicarboxylic acid hydrazide composition with low levels of hydrazine, well below the 1 ppm limit. As used herein, the term dicarboxylic acid hydrazide encompasses any dicarboxylic acid hydrazide salt described in the present invention. These include any dicarboxylic acid selected from, but not limited to, maleic acid, citric acid, oxalic acid, succinic acid, malonic acid, adipic acid, italic acid, terephthalic acid, and combinations thereof. As used herein, the term transition metal ion refers to the ions of the metallic elements listed in the periodic table as transition metals, which have a positive valence state. The metal ions are selected from, but not limited to, copper, iron, zinc, cobalt, nickel, silver, vanadium, chromium, manganese, mercury, scandium, titanium, tungsten, cadmium, platinum, rhodium, palladium, molybdenum, osmium, ruthenium, zirconium, gold, or combinations thereof. The valence state can range from +1 to +n, where n denotes infinity. As used herein, the expression hydrazine levels refers to the hydrazine content quantified by the standard method of GCEM (gas chromatography coupled to mass spectrometry). The term acceptable quantity in agriculture refers to an amount of an active agent that eliminates or inhibits the plant disease / condition that is to be controlled, in an amount that is not significantly toxic to the plant being treated. Therefore, in one embodiment, the present invention provides a composition comprising: a) at least one compound selected from a dicarboxylic acid hydrazide; and b) at least one transition metal ion or a salt thereof. According to a preferred embodiment, the dicarboxylic acid is maleic acid and the hydrazide of maleic acid is maleic hydrazide. In one embodiment, the preferred transition metal ions are copper, iron, nickel, or combinations thereof. More specifically, the preferred transition metal ions are Cu2+, Cu3+, Fe2+, Fe3+, Ni2+, Ni3+, or combinations thereof. Another embodiment of the present invention provides a composition comprising maleic hydrazide and at least one transition metal ion or salt thereof. Such compositions have been shown to be stable during storage. As another embodiment, said transition metal ion may be selected from the group of copper, nickel, iron, or a combination thereof. In a preferred embodiment, the metal is copper. In one embodiment, the level of hydrazine in the composition can be kept below 1 ppm, preferably less than 28 ppm, more preferably less than 16.8 ppm, most preferably less than 4.6 ppm. An embodiment of the present invention provides a composition comprising maleic acid hydrazide and transition metal ions selected from copper, iron, and nickel or salts thereof, or a combination thereof. In a preferred embodiment, the transition metal is copper. According to one embodiment, these transition metals or their ions can be introduced into the composition as metallic salts. Types of salts include sulfates, sulfites, sulfides, chlorates, chlorites, chlorides, halides, nitrates, nitrites, carbonates, bicarbonates, persulfates, dichromates, bisulfates, permanganates, chromates, acetates, citrates, cyanides, hydroxides, oxides, phosphates, dichlorates, or combinations thereof. According to one embodiment, the amount of transition metal ions in the liquid composition can range from 0.1 ppm to 1000 ppm, preferably from 0.1 ppm to 125 ppm, more preferably from 0.1 to 2 ppm. According to one embodiment, the amount of transition metal ions in the αζη / ι ηζζηζ-ΐ / γίΛΐ solid composition can range from 0.1 ppm to 1000 ppm, preferably from 125 ppm to 1000 ppm. In one embodiment, the hydrazine level in the final product can be maintained at less than 1 ppm, preferably less than 28 ppm, more preferably 16.8 ppm, and most preferably 4.6 ppm or less. The final composition can remain stable during storage within the stated specification of the hydrazine level below 1 ppm, preferably less than 28 ppm, more preferably 16.8 ppm, preferably 4.6 ppm or less for a period of up to 2 years. According to another embodiment, the composition of the present invention may further comprise excipients acceptable in agriculture, such as adjuvants, surfactants, colorants, thickeners, antifreeze agents, biocides, antifoaming agents, stabilizers, wetting agents, or a mixture thereof, which may optionally be added to the compositions of the present invention. Therefore, in one embodiment, the surfactants can be selected from non-ionic, anionic, or cationic surfactants. Examples of nonionic surfactants include polyarylphenol polyethoxy ethers, polyalkylphenol polyethoxy ethers, polyglycol ether derivatives of saturated fatty acids, polyglycol ether derivatives of unsaturated fatty acids, polyglycol ether derivatives of aliphatic alcohols, polyglycol ether derivatives of cycloaliphatic alcohols, polyoxyethylenesorbitan fatty acid esters, alkoxylated vegetable oils, alkoxylated acetylenic diols, polyalkoxylated alkylphenols, fatty acid alkoxylates, sorbitan alkoxylates, sorbitol esters, C8-C22 alkyl or alkenyl polyglucosides, polyalkoxystyrylyl ethers, alkylamine oxides, block copolymer ethers, polyalkoxylated fatty glyceride, polyalkylene glycol ethers, aliphatic polyesters, or linear aromatics, organosilicones, polyaryl phenols, sorbitol ester alkoxylates, polyalkylene oxide block copolymers,acrylic copolymers and ethylene glycol mono- and diesters and mixtures thereof. Examples of anionic surfactants include alcohol sulfates, alcohol ether sulfates, alkyl ether sulfates, alkylaryl sulfonates such as alkylbenzene sulfonates and alkylnaphthalene sulfonates and their salts, alkyl sulfonates, mono- or diphosphate esters of polyalkoxylated alkyl alcohols or alkylphenols, mono- or disulfosuccinate esters of C12-C15 alkandes or alkandes. C12-C15 polyalkoxylates, alcohol ether carboxylates, phenolic ether carboxylates, polybasic acid esters of ethoxylated polyoxyalkylene glycols consisting of oxybutylene or the tetrahydrofuran residue, sulfoalkylamides and their salts, such as N-methyl-N-oleoyltaurate salt Nade, polyoxyalkylene alkylphenol carboxylates, alkyl alcohol polyglucoside carboxylates / alkenylsuccinic anhydride condensation products, alkyl ester sulfates, naphthalene sulfonates, naphthalene formaldehyde condensates, alkyl sulfonamides, sulfonated aliphatic polyesters, alkoxylated styrylphenyl sulfate esters and alkoxylated styrylphenyl sulfonate esters, and their corresponding sodium, potassium, calcium salts, magnesium, zinc, ammonium, alkylammonium, diethanolammonium or triethanolammonium, salts of lignisulfonic acid, such as sodium, potassium, magnesium, calcium or ammonium salts,polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates, and sulfated alkyl phenol ethoxylates and phosphated alkyl phenol ethoxylates. Cationic surfactants include C8C18 fatty acid alkanol amides and C8-C18 fatty amine polyalkoxylates, C10-C18 alkyl dimethylbenzylammonium chlorides, coconut alkyldimethylaminoacetic acids, and phosphate esters of C8-18 fatty amine polyalkoxylates. In one embodiment, the colorants can be selected from iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes or metallic phthalocyanine dyes, and trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. Another embodiment involves the addition of a thickener or binder which may be selected, but is not limited to, molasses, granulated sugar, alginates, karaya gum, guar gum, tragacanth gum, polysaccharide gum, mucilage, xanthan gum or a combination thereof. In another embodiment, the binder can be selected from silicates such as magnesium aluminum silicate, polyvinyl acetates, polyvinyl acetate copolymers, polyvinyl alcohols, polyvinyl alcohol copolymer, celluloses, including ethylcelluloses and methylcelluloses, hydroxymethylcelluloses, hydroxypropylcelluloses, hydroxymethylpropylcelluloses, polyvinylpyrrolidones, dextrins, maltodextrins, polysaccharides, fats, oils, proteins, gum arabic, shellac, vinylidene chloride, vinylidene chloride copolymers, calcium lignosulfonates, acrylic copolymers, starches, polyvinyl acrylates, zeins, gelatin, carboxymethylcellulose, chitosan, polyethylene oxide,Polymers and copolymers of acrylimide, polyhydroxyethyl acrylate, methylacrylimide monomers, alginate, ethylcellulose, polychloroprene, and syrups or mixtures thereof; polymers and copolymers of vinyl acetate, methylcellulose, vinylidene chloride, acrylic, cellulose, polyvinylpyrrolidone, and polysaccharide; polymers and copolymers of vinylidene chloride and vinyl acetate-ethylene copolymers; combinations of polyvinyl alcohol and sucrose; plasticizers such as glycerol, propylene glycol, and polyglycols. In another embodiment, the antifreeze agent or agents added to the composition may be alcohols selected from the group comprising, but not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,3-dimethyl-2,3-butanediol, trimethylol propane, mannitol, sorbitol, glycerol, pentaerythritol, 1,4-cyclohexanedimethanol, xylenol, bisphenols such as bisphenol A or similar. In addition, ether alcohols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyoxyethylene or polyoxypropylene glycols of molecular weight up to approximately 4000, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, butoxyethanol, butylene glycol monobutyl ether, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol. According to one embodiment, the biocides can be selected from benzothiazoles, 1,2-benzothiazolin-3-one, dichloro-s-triazinetrione sodium, sodium benzoate, potassium sorbate, 1,2-phenylisothiazolin-3-one, interchloroxylenol butyl paraoxybenzoate. According to one embodiment, the antifoaming agent can be selected from polydimethoxysiloxane, polydimethylsiloxane, alkyl polyacrylates, castor oil, fatty acids, fatty acid esters, fatty acid sulfate, fatty alcohol, fatty alcohol esters, fatty alcohol sulfate, olive oil, mono- and diglycerides, paraffin oil, paraffin wax, polypropylene glycol, silicone oil, vegetable and animal fats, vegetable and animal fat sulfate, vegetable and animal oil, vegetable and animal oil sulfate, vegetable and animal wax, vegetable and animal wax sulfate.According to one embodiment, the composition can be applied to selected target crops from among tobacco, potato, onion, ascalonia, strawberries, raspberries, stone fruits, cranberries, blackberries, blueberries, gooseberries, tubers, carrot, citrus, beans, beetroot, corn, lima beans, peas, swede, sugar beetroot, garlic, tomato, floriculture and horticulture. In one embodiment, the potential uses of the composition include its use as a plant growth inhibitor, plant growth regulator, plant growth promoter, defoliant, shoot inhibitor, seed treatment, flowering agent, fruiting agent, nutrient, and fertilizer. The composition can be applied to the target crop by spraying, misting, dusting, coating, hand application, or as an aerosol. In one embodiment, the application rates for a solid formulation are in the range of 2.5-5.0 of product / ha (equivalent to 1.5-3.0 kg of maleic hydrazide / ha) and for the liquid formulation in the range of 11.0-17.5 l / ha (equivalent to 2.05-3.26 kg of maleic hydrazide / ha). Another embodiment of the present invention may involve the use of transition metal ions to control and maintain the levels of free hydrazine in a composition below 1 ppm, preferably below 28 ppm, more preferably below 16.8 ppm, and most preferably below 4.6 ppm. The use of transition metal ions renders the composition low in toxicity and confers stability. The transition metal ions used in the composition can be copper, iron, nickel, or a combination thereof; copper ions are most preferred. The metal ions can be introduced into the composition as metal salts. Dicarboxylic acid hydrazides can be selected from maleic hydrazide, citric hydrazide, oxalic hydrazide, succinic hydrazide, malonic hydrazide, adipic hydrazide, italic hydrazide, and terephthalic hydrazide. Maleic hydrazide is preferred. In one embodiment, the composition of the present invention can be formulated as a liquid or solid composition. It can be formulated as a powder (DS), a powder suspended in water (WS), a non-aqueous solution (LS), dry liquid pastes (DF), free-flowing liquids (LF), true liquids (TL), emulsifiable concentrates (EC), fine powders (D), wettable powders (WP), suspensions (SE), soluble concentrates (SL), water-soluble granules (SG), water-dispersible granules (WG), or a fluid suspension (FS). In one embodiment, transition metal ions can be used to control hydrazine levels in the technical dicarboxylic acid hydrazide, wherein the technical dicarboxylic acid hydrazide is substantially hydrazine-free. The hydrazine levels of the technical dicarboxylic acid hydrazide can be maintained below 1 ppm, preferably below 28 ppm. The preferred technical dicarboxylic acid hydrazide is maleic hydrazide, and the transition metal ion can be selected from copper, iron, nickel, or a combination thereof. Copper is the preferred transition metal ion. In another embodiment, technical dicarboxylic acid hydrazide with hydrazine levels below 1 ppm, preferably less than 28 ppm, can be used in the preparation of the composition comprising dicarboxylic acid hydrazide and at least one transition metal ion. In a preferred embodiment, maleic hydrazide with hydrazine levels below 1 ppm, preferably less than 28 ppm, can be used in a composition comprising maleic hydrazide and at least one transition metal ion. The transition metal ion can be selected from copper, iron, nickel, or a combination thereof. Copper is the preferred transition metal ion. In one embodiment, the present invention may include a method for preparing a solid composition comprising: A) Dissolve the transition metal salts in water to obtain the desired concentration of metal ions in the solutions; B) add the technical dicarboxylic acid hydrazide to said solution to form a suspension; C) mix, filter and dry said suspension. In one embodiment, it may include a method of preparing a liquid composition comprising: combining water and transition metal ions; adding said water to dicarboxylic acid hydrazides. In one embodiment, soft water is used. As used herein, the term "soft water" refers to water with less than 17.1 mg / l ppm or 1 grain / gal of calcium and / or magnesium ions, or hard water that has been treated by a process in which the calcium and magnesium ions are removed or replaced by sodium ions. Hard water is characterized by the presence of calcium and / or magnesium ions in the form of salts with a concentration of 17.1 mg / l ppm and above, or 1 grain / gal and above. The process used to convert hard water into soft water can be achieved through the use of precipitation water softeners (sodium carbonate, borax), ion exchange with sodium ions for the softening process (the sodium ions in the ion exchange resin displace the calcium and magnesium ions present in the water), the addition of chelating agents such as EDTA, or by subjecting the water to a distillation or reverse osmosis process and / or adsorption filtration. The preferred method is ion exchange with sodium ions for the softening process. As used herein, the term "maximum permissible level" refers to the maximum amount of metal ions allowed in drinking water. The specifications for the maximum permissible level are given in Table 1. Table 1: Permissible quantities of metal ions added to drinking / softened water αζη / ίη / ζζηζα / γίΛΐ Element Specification (ppm) Minimum Maximum Copper (Cu2+) 1.5 2.0 Calcium (Ca2+) - 1 Magnesium (Mg2+) - 0.1 Sodium (Na2+) - 200 The process mentioned above may have the following advantages: it degrades the hydrazine in the final formulated product and the hydrazine levels can be controlled within the specified limit of 1 ppm, preferably less than 28 ppm, more preferably less than 16.8 ppm, most preferably 4.6 ppm; the use of EDTA may not be necessary; crystallization of the product may not occur; it provides a stable composition with a significant shelf life. In one embodiment, the composition is physically stable with a free hydrazine level of less than 1 ppm, preferably less than 28 ppm, more preferably 16.8 ppm, most preferably 4.6 ppm, for a period of up to 2 years. The transition metal ions used in the aforementioned composition can be copper, iron, or nickel; copper ions are more preferably used. The metal ions can be introduced into the composition as metal salts. Dicarboxylic acid hydrazides may be selected from maleic hydrazide, citric hydrazide, oxalic hydrazide, succinic hydrazide, malonic hydrazide, adipic hydrazide, italic hydrazide, and terephthalic hydrazide. Maleic hydrazide is preferred according to one embodiment. An embodiment of the present invention may encompass a method of preparing a liquid composition comprising: combining soft water and transition metal ions, wherein the transition metal ions are added up to a maximum permissible level; adding said combination to maleic hydrazide. In one embodiment, the transition metal ions used in the composition can be copper, iron, or nickel; more preferably copper ions. The transition metal ions can be introduced into the composition as metal salts. The amount of copper ions added to the composition can range from 1.5 ppm to 2.0 ppm. The above-mentioned composition may contain a hydrazine level of less than 1 ppm, preferably less than 28 ppm, more preferably 16.8 ppm, preferably 4.6 ppm, and may be stable during storage for up to 2 years. In a further embodiment, the present invention provides a method of treating a plant in a location by applying a low-toxicity composition comprising: at least one compound selected from a dicarboxylic acid hydrazide, and at least one transition metal ion. The above-mentioned composition may contain a hydrazine level of less than 1 ppm, preferably less than 28 ppm, more preferably 16.8 ppm, preferably 4.6 ppm, and may be stable during storage for up to 2 years. The transition metal ion can be copper, iron, nickel, or a combination thereof; copper ions are more preferred. The metal ion can be introduced in the form of metal salts. Dicarboxylic acid hydrazides can be selected from maleic hydrazide, citric hydrazide, oxalic hydrazide, succinic hydrazide, malonic hydrazide, adipic hydrazide, italic hydrazide, and terephthalic hydrazide. Maleic hydrazide is preferred. In one embodiment, the composition of the present invention can be formulated as a liquid or solid composition. It can be formulated as a powder (DS), a powder suspended in water (WS), a non-aqueous solution (LS), dry liquid pastes (DF), free-flowing liquids (LF), true liquids (TL), emulsifiable concentrates (EC), fine powders (D), wettable powders (WP), suspoemulsions (SE), soluble concentrates (SL), water-soluble granules (SG), water-dispersible granules (WG), or a fluid suspension (FS). The treated plant can be selected from tobacco, potato, onion, strawberries, raspberries, stone fruits, cranberries, blackberries, blueberries, gooseberries, tubers, carrot, citrus fruits, beans, beetroot, corn, lima beans, peas, swede, ascalonia, sugar beetroot, garlic, tomato, floriculture, and horticulture. The compositions can be used in seed treatment, where the composition can be applied to plant propagation material. As used herein, the term "plant reproductive material" encompasses any tissue of plant origin used in the vegetative reproduction or cultivation of a plant, seedling, or any part of a plant. This includes seeds, grains, husks, seed coats, roots, shoots, tubers, rhizomes, bulbs, corms, anthers, stamens, pollen, stigmas, fruits, flowers, buds, bark, stems, blades, tendrils, pods, etc. Treatment of the aforementioned plant may be achieved by applying such material before or after emergence. In addition to the aforementioned benefits of the composition of the present invention, the use of transition metal ions provides the advantage of making the composition less phytotoxic to the plant to which it is applied, less hazardous to the consumer through direct exposure to the product, and indirectly less harmful to the end user of the plant to which it is applied. It also has the advantage of being less toxic to adjacent flora and fauna, thus not endangering neighboring species and beneficial animals with the potent toxin. In another embodiment, the composition of the present invention is effective against the pests of the crops mentioned above, such as sucking pests. In another embodiment, the composition of the present invention is an effective anti-budding agent. In yet another embodiment, the composition of the present invention is an effective growth regulator that provides increased yield and vigor. In one embodiment, a composition according to the present invention αζη / ι ηζζηζ-ΐ / γίΛΐ can be a solid composition. In one embodiment, the amount of a metal ion in the compositions of the present invention may be less than, or approximately, 1 ppm. In one embodiment, the amount of a metal ion in the compositions of the present invention may be less than, or approximately, 2 ppm. In one embodiment, the amount of a metal ion in the compositions of the present invention may be less than, or approximately, 125 ppm. In one embodiment, the compositions of the present invention are in the form of maleic hydrazide 600 SG, maleic hydrazide 186.5 SL, or maleic hydrazide 270 SL. In one embodiment, the present invention provides technical material of maleic hydrazide having less than 28 ppm of hydrazine as a contaminant. One embodiment of the present invention is the formulation of maleic hydrazide 600 SG having less than 16.8 ppm of hydrazine. Another embodiment of the present invention is maleic hydrazide 186.5 SL or 270 SL having less than 4.6 ppm of hydrazine. In one embodiment, the composition of the invention comprises approximately 0.05 wt% copper(n) sulfate pentahydrate. In one embodiment, copper or its salts can be added to the water used to prepare the composition instead of being added externally to it. In one embodiment, the water used for the preparation of the composition comprises approximately 2 ppm of copper. In one embodiment, the solid compositions comprise copper between 125 ppm and approximately 1000 ppm of copper or its salts. In one embodiment, the solid composition of the present invention can be administered to the desired site in the range of 2.5-5.0 kg of product / ha (equivalent to 1.5-3.0 kg of maleic hydrazide / ha). In this embodiment, the composition comprises approximately 80.4% by weight of potassium salt of maleic hydrazide, equivalent to 60% pure maleic hydrazide. In one embodiment, the liquid composition of the present invention can be applied to the desired site at a rate of 11.0–17.5 L / ha (equivalent to 2,053.26 kg of maleic hydrazide / ha). In one embodiment, the process for preparing the composition of the present invention comprises neutralizing the maleic hydrazide αζη / Ln / zznz / 3 / γΐΛΐ with an alkali metal hydroxide. In one embodiment, the alkali metal hydroxide is potassium hydroxide. The present invention is explained more specifically by the examples provided above. However, it should be understood that the scope of the present invention is in no way limited by the examples. Any person skilled in the art will appreciate that the present invention includes the examples provided and, furthermore, can be modified and altered without departing from the novel lessons and advantages of the invention that are intended to be included within the scope of the invention. Example 1: Diagram 1: Maleic hydrazide manufacturing process αζη / ίη / ζζηζα / γίΛΐ 1. H2SO4 2. NaOH h2n'NH2(H2O) Maleic anhydride Hydrazine PM: 98.06 PM: 32.05 Maleic hydrazide PM: 112.09 Copper sulfate is dissolved in 100 ml of water, obtaining the desired concentration of Cu(II) ions in the solutions. To this, 10 g of technical grade maleic hydrazide are added, forming a suspension. The mixture is stirred for 10 minutes at room temperature. It is then vacuum filtered for 5 minutes and dried at 60 °C for 24 hours. The hydrazide content in the technical maleic hydrazide obtained in this way was analyzed as a function of the different levels of copper present in the washing water. Results % Copper Hydrazine Content (ppm) Comments Untreated 24.5 Initial Hydrazine Level White 9.8 100 ml of water, copper-free 0.0002% 10.4 0.001% 4.5 0.01% 3.1 0.1% 3.0 0.5% 2.9 1% 2.7 10% < LDQ αζη / ι ηζζηζ-ΐ / γίΛΐ Thus, it was observed that washing the MH with water was an effective method for reducing hydrazine, lowering the level from 24.5 ppm to ~10 ppm. It was also found that increasing the water washing step resulted in a substantial reduction of the hydrazine level, from 10 ppm to ~5 ppm. Therefore, in one embodiment, the present invention provides a process for preparing maleic hydrazide, said process comprising: (a) mix maleic anhydride, hydrazine and sulfuric acid in water; and (b) add copper sulfate to the resulting suspension. In one embodiment, the present invention provides a process for preparing maleic hydrazide, said process comprising: (a) mix maleic anhydride, hydrazine and sulfuric acid in water at an elevated temperature; (b) add a base to adjust the pH; and (c) add copper sulfate to the resulting suspension. In one embodiment, the present invention provides a process for preparing maleic hydrazide, said process comprising: (a) mix maleic anhydride, hydrazine and sulfuric acid in water at an elevated temperature; (b) add a base to adjust the pH; (c) add copper sulfate to the resulting suspension; (d) shake the suspension at room temperature for 30 minutes; (e) centrifuge the suspension to remove water; and (f) dry at high temperature. Several experimental tests of this process have been carried out and the following observations have been made: Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Test 7 Test 8 Test 9 Test 10 Maximum temperature 90 90 93 91 100 95 92 97 95 96 Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Test 7 Test 8 Test 9 Test 10 liquid KOH reaction No No No Yes No Yes Yes Yes Yes Yes No Air purge Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes CuSO 4 No No No No Yes (1000 ppm) Yes (1000 ppm) Yes (1000 ppm) Yes (250 ppm) Yes (125 ppm) Yes (250 ppm) Reaction time 30 min 30 min 30 min 30 min 30 min 30 min 30 min 30 min 30 min Solid KOH addition 100 % 100 o / / o 100 o / / o 50 % 100 % 80 % 50% 80 % 80 % 100 o / / o Addition of liquid KOH at 50% 0% 0% 0% 50% 0% 20% 50% 20% 20% 0% Addition of KOH 20 min 20 min 20 min 20 min 20 min 20 min 20 min 20 min 20 min Drying time 0 60 min 60 min 60 min 60 min 60 min 60 min 60 min 60 min 60 min 60 min Temp.of drying 0 110 g 110 g 110 g 110 g 110 g 110 g 110 g 110 g 110 g 110 g LDD of drying 0 <1.0 % <1.0 % <1.0 % <1.0 % <1.0 % <1.0 % . <1.0 % <1.0 % <1.0 % <1.0 % Notes Are giving Are giving CuSO 4 (1000 PPm) added do to the initial charge of liquid KOH 0 + CuSO 4 80:20 (1000 PPm) liquid KOH 0 + CuSO 4 50:50 (1000 PPm) liquid KOH 0 + CuSO 4 80:20 (250 PPm) Liquid KOH 0 + CuS 04 80:20 (125 ppm). Prue 1 Prue 2 Prue 3 Prue 4 Prue 5 Prue 6 Prue 7 Prue 8 Prue 9 Prue 10 agua Parám etro Prue 1 Prueb a 2 Prue 3 Prue 4 Prue 5 Prue 6 Prue 7 Prue Prue ba 9 Liquid KOH No No No Yes No Yes Yes Yes Yes Yes Air Purge Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes CuSO 4 No No No No Yes (1000 ppm) Yes (1000 ppm) Yes (1000 ppm) Yes (250 ppm) Yes (125 ppm) Hydrazi granule or finish and 147,101,101,310 <5.9 ndnd <5.9 <5.9 αζη / ίη / ζζηζα / γίΛΐ Thus, it was found that regulating the pH of the suspension and adding copper salts allowed for a surprising reduction in the hydrazine content, even below the regulatory threshold. Therefore, a reprocessing procedure was established for technical grade maleic hydrazide: After adding deionized water (6233 g) to the wet product, a sodium hydroxide solution is added at 60 °C until a clear, yellowish solution is obtained. The typical amount of sodium hydroxide solution for complete dissolution (24%, 2020 g, 12.12 mol) results in a pH of 7.0–8.0 (at 60 °C). Subsequently, sulfuric acid (96%, 668 g, 6.54 mol) is added until the pH reaches the range of 2.0–2.5 (at 60 °C). The suspension is cooled to room temperature and the product is filtered. A double replacement wash is performed with deionized water (1558 g each), and the wet product is dried to obtain a crystalline solid. The maleic hydrazide produced in this way was used to prepare the compositions of the invention and was compared with comparative compositions without the copper salts. | | Test 1 / ST 4602 / | Test 9 / ST4603 / | G1808ad Standard Fazor G1808ae Fazor with 125 ppm copper Prueba GRL13202 LPG Result (Specific action) Initial 2W5 4 015 0 024 0 03 25 Initial 2W5 4 015 0 024 0 03 25 Color and appearance Beige granule with free flow No beig granule with free flow No beig granule with free flow No beig granule with free flow No beig granule with free flow NE No beig granule with free flow NE No beig granule with free flow No beig granule with free flow NE no beig granule with free flow NE Content of water (<1%) 0.21 o / / o 0.28 o / / o 0.22 o / / o 0.29 % NE 0.64 % 0.61 o / / o 0.54 % 1.04 % NE pH (2 % solution) 9.6 (8-11.5) 10.4 10 1 9.6 9.6 / 9.3 (1 %) NE 7.7 7.4 7.5 7.6 / 7.4 (1 %) NE Persistent foam (mi tras 1 min) 19-24 mi (<35 mi) 25 30 13 12 NE 5 5 13 3 NE Hydrazine (ppmm ) <16.8 pp mm 182, 32 205, 9 220 224, 6 22 0.4 <1 13.5 7.85 11.8 It was found that the compositions of the invention presented a favorable neutral pH, and substantially lower amounts of persistent foam and hydrazine content. Example 2: Several comparative compositions were prepared with other hydrazine regulating agents and their content was analyzed. Sample Name Storage Composition Hydrazine Content (ppmm, w / w Al) Maleic Hydrazide 270SL Reference Temperature 3.2 2W54 °C 144.4 αζη / ι ηζζηζ-ΐ / γίΛΐ Maleic hydrazide 270SL 25 °C 2 ppm Cu2+ Not detected 2W54 °C Not detected Maleic hydrazide 270SL 25 °C lOOOppmNaOCI 72.6 2W54 °C 247.4 Maleic hydrazide 270SL 25 °C 1000 ppm H2O2 184.3 2W54 °C 65.1 Maleic hydrazide 270SL 25 °C 1000 ppm a-ketoglutaric acid Not detected 2W54 °C 83.3 Maleic hydrazide 270SL 25 °C 1000 ppm maleic anhydride Not detected 2W54 °C 119.6 25 °C reference Not detected Maleic hydrazide 186.5SL 2W54 °C 153.6 αζη / ίη / ζζηζα / γίΛΐ Therefore, it was concluded that copper salts, additionally in the presence of an alkali metal hydroxide, besides reducing the hydrazine content of the resulting final formulations, also substantially improved the 5 physicochemical properties of the resulting solid or liquid formulations. Example 3: Storage stability was demonstrated by testing the levels of hydrazine generated over a period of up to 12 months. Samples were stored at temperatures of -10 °C, 0 °C, 25 °C, 40 °C, 50 °C, and 10–54 °C. The tests were performed at two geographically different locations. Formulation: Maleic hydrazide 270 SL with 125 ppm of copper The formulation remained a clear, homogeneous liquid in appearance after 1 month at 4 °C, after 2 months at 10 °C, and would become homogeneous upon thawing of the frozen samples. Initial Interval 2 weeks 1 month 2 months 3 months 6 months Temp (°C) N / A 10 54 40 50 10 40 50 0 25 40 0 25 40 Content Det. (% w / w) 22.9 5 23.04 22.9 5 22.98 22.93 23.00 Phase Separation 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (%) Sediment (S / N) NNNNNNNNNNNNNN Pure pH 9.0 8.8 8.9 9.2 9.1 9.0 9.0 9.0 9.0 9.0 9.0 9.1 9.1 9.0 Hydrazine Content Specification <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 <6.3 Hydrazine Content Location n.9 1 (ppmm in formulated product) 2.50 7.5 6 5.20 2.08 3.47 2.9 4 3.5 6 Hydrazine Content Location n.9 2 (ppmm in formulated product) ) <3.1 (LD C) <3.1 (LD C) <LD D (0,0 35) <LD D (0,0 35) <3, 1 (LD C) <3, 1 (LD C) αζη / ίη / ζζηζα / γίΛΐ Formulation: Maleic hydrazide 186.5 SL comprising 100 ppm of copper (Location n.e1) The particles of the formulation remained in suspension throughout the 5 storage period and no change was observed. Initial Interval 2 weeks 1 month 2 months 3 months 6 months 12 months Temp (°C) N / A 1 0 5 4 40 50 -10 4 0 5 0 0 25 4 0 0 2 5 4 0 0 25 Det. of content (% w / w) 16.5 1 6. 5 1 6. 5 16.5 1 6. 5 Sediment NSSSSSSSSSSSSSSS (S / N) pH 1 % 9.2 9.2 9.2 9.2 9.2 9.2 9.1 9.2 9.0 9.0 9.1 9.1 9.2 9.0 9.0 9.1 9.1 Hydrazine Content Specification <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 <4.6 Hydrazine Content Location ne 1 (ppmm in formulated product) 0 4.0 4.0 <L D C (3, 1) No dete ctad a No dete ctad a 1, 3 3, 2 No dete ctad a No dete ctad a 1, 6 No dete ctad a 3 2 3, 3 <L D C (3, 1) <L D C (3, 1) αζη / ίη / ζζηζα / γίΛΐ Formulation: Maleic hydrazide 186.5 SL comprising 100 ppm of copper (Location n.e2) The particles of the formulation remained in suspension throughout the 5 storage period and no change was observed. Initial Interval 2 weeks 1 month 2 months 3 months 6 months 12 months Temp (°C) N / A -10 54 4 0 50 -10 4 0 5 0 0 25 40 0 2 5 4 0 0 2 5 Det. of content (% w / w) 16.6 1 16.7 7 1 6, 6 3 16.8 16.8 Sediment (S / N) SSSSSSSSSSSSSSSS pure pH 8.8 8.8 9.0 8, 8 8.8 8.8 8, 8 8, 7 8.7 8.8 8.8 8.8 8 5 7 8 5 8 8, 8 8, 8 Conte specification <4, 6 <4, 6 <4, 6 σ> 4* λ <4, 6 <4, 6 < 4, 6 < 4, 6 <4, 6 <4, 6 <4, 6 <4, 6 < 4, 6 < 4, 6 < 4, 6*Λ Initial Interval 2 weeks 1 month 2 months 3 months 6 months 12 months hydrazine nest Hydrazine content Location n.9 2 (ppm m in formulated product) Not detected Not detected Not detected < LOC (3,1) Not detected Not detected < LDC (3 ,1 ) < LDC (3 ,1 ) Not detected Not detected Not detected Not detected 3 2 3 5 3 < LDC (3 ,1 ) < LDC (3 ,1 ) αζη / ίη / ζζηζα / γίΛΐ Example 4: The compositions of the present invention were applied to different crops to verify their effectiveness. The compositions were intended for use as anti-budding agents, growth regulators, and for pest control. Anti-budding activity The two formulations, 270 SL and 60 SG, were applied to potatoes, and sprouting efficacy was recorded at 121, 152, 181, 211, and 241 days after the 10th application. 270 SL was applied at different doses and in two different formulations. Days after the first / last application. 121 152 181 211 241 Treatment No. Treatment Name 0 Application Rate Rate Unit Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots 1 Untreated control 3.5 22.5 20.3 19.3 23 2 Formulation 270 SL nQ 1 7.77 l / ha 1 19 17.5 13.8 16 3 Formulation 270 SL n.9 1 11.1 l / ha 0.5 16 14 9.5 12.5 Days after the first / last application. 121 152 181 211 241 Treatment No. Treatment Name 0 Application Rate Rate Unit Number of Shoots Number of Shoots Number of Shoots Number of Shoots Number of Shoots 4 Formulation 270 SL na 1 22.2 l / ha 0 15.5 8.5 4.3 6 5 Formulation 270 SL na 2 7.77 l / ha 2 18 16.5 10.5 14 6 Formulation 270 SL na 2 11.1 l / ha 0.8 14 10.8 7 9 7 Formulation 270 SL na 2 22.2 l / ha 0 11.3 7 2 3.3 8 Formulation 60 SG 5 kg / ha 0.5 15.3 13 8.3 10.8 9 Formulation 60 SG 10 kg / ha 0.3 11.8 7.5 3 5.5 αζη / ίη / ζζηζα / γίΛΐ The two formulations, 270 SL and 60 SG, were applied to onions, and sprouting efficacy was recorded at 93, 122, and 184 days after application. 270 SL was applied at different doses and in two different formulations. The experiment was conducted on two batches of onions. Days after first / last application 93 (lot 1) 93 (lot 2) 122 (lot 1) 122 (lot 2) 184 (lot 1) 184 (lot 2) Treatment No. Treatment Name Application Rate Rate Unit Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots 1 Untreated control 12.8 4.5 23.3 4.8 4.8 10.8 2 Formulation 270 SL ns 1 6.23 l / ha 7.8 1 17.8 3.3 1 5.8 3 Formulation 270 SL na 1 8.9 l / ha 5.8 1 15.3 2.5 2.3 6.3 4 Formulation 270 SL na 1 17.8 l / ha 4.5 0.5 10.8 1 1.8 2.8 5 Formulation 270 SL na 2 6.23 l / ha 6 1.3 17.3 4 2.S 3.5 Days after first / last application 93 (lot 1) 93 (lot 2) 122 (lot 1) 122 (lot 2) 184 (lot 1) 184 (lot 2) Treatment No. Treatment Name Application Rate Rate Unit Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots 6 Formulation 270 SL n.2 2 8.9 l / ha 4.3 0.3 11.8 2.3 2.3 5 7 Formulation 270 SL nQ 2 17.8 l / ha 2.3 1 5 0.3 1.5 1 8 Formulation 60 SG 4 kg / ha 5.8 1.3 13.5 1.8 3 6.8 9 Formulation 60 SG 8 kg / ha 2 0.8 8 0.5 2.3 3.5 αζη / ίη / ζζηζα / γίΛΐ The two formulations 270 SL and 60 SG were applied to garlic and the effectiveness of sprouting was recorded at 60, 93, 122, 151 and 184 days after application. 270 SL was applied in different doses and in two different formulations. Days after first / last application 60 93 122 151 184 Treatment No. Treatment Name 0 Application Rate Rate Unit Number of shoots Number of shoots Number of shoots Number of shoots Number of shoots 1 Untreated control 2.3 12.8 23.3 32.5 55.8 2 Formulation 270 SL n.2 1 6.23 l / ha 1.3 7.8 17.8 27.8 43.8 3 Formulation 270 SL n.2 1 8.9 l / ha 1.3 5.8 15.3 24.5 37 4 Formulation 270 SL n.2 1 17.8 l / ha 0.5 4.5 10.8 17.8 29.8 5 Formulad ón 270 SL n.2 2 6.23 l / ha 1.5 6 17.3 28 43 6 Formulad ón 270 SL n.2 2 8.9 l / ha 1 4.3 11.8 23.5 36.5 7 Formulad ón 270 SL n.2 2 17.8 l / ha 0.5 2.3 5 12.3 27.5 8 Formulation 60 SG 4 kg / ha 0.8 5.8 13.5 24.3 38.3 9 Formulation 60 SG 8 kg / ha 0.3 2 8 14.3 28.5 αζη / ίη / ζζηζα / γίΛΐ Growth regulator The two formulations 270 SL and 60 SG were applied to potatoes and onions as a growth regulator and the number of bulbs was counted after 181 days and 152 days after application, respectively. Crop Potato Onion Days after first / last application 181 152 Treatment No. 0 Treatment Name Application Rate Rate Unit Number of Bulbs Application Rate Rate Unit Number of Bulbs 1 Untreated Control 7 5.5 2 Formulation 270 SL na 1 7.77 l / ha 12 6.23 l / ha 2 3 Formulation 270 SL na 1 11.1 l / ha 18.5 8.9 l / ha 4.3 4 Formulation 270 SL na 2 7.77 l / ha 14 6.23 l / ha 2.8 5 Formulation 270 SL na 2 11.1 l / ha 22.5 8.9 l / ha 4 6 Formulation 60 SG 10 kg / ha 28.8 4 kg / ha 4.3 Pest control: The 270 SL formulation was applied to tobacco in two variants and at two different rates. The effect was verified in the reduction of the number of sucking pests and the yield. Treatment No. Treatment Application Rate Rate Unit Number of sucking pests in tobacco Yield 1 untreated control 103 0.1 Treatment No. Treatment Application Rate Rate Unit Number of sucking pests in tobacco Yield 3 Formulation 270 SL nQ 1 10 l / ha 20 1.7 4 Formulation 270 SL ne 1 20 l / ha 14 1.4 6 Formulation 270 SL nQ 2 10 l / ha 15.5 1.5 7 Formulation 270 SL n.2 2 20 l / ha 11.8 1.7 8 Formulation 80 SG 4.5 kg / ha 28.3 2.5 αζη / ίη / ζζηζα / γίΛΐ It was further discovered that the introduction of a transition metal ion or its salt led to a substantial improvement in the sprout-inhibiting activity of maleic hydrazide. This was corroborated by several field experiments, demonstrating the efficacy of maleic hydrazide in sucker suppression in tobacco and in sprout inhibition in potato, onion, and garlic. These experiments showed that the efficacy depended on the presence or absence of the transition metal ion or its salt. Surprisingly, it was observed that in the presence of a transition metal ion or its salt, the efficacy of maleic hydrazide in sucker suppression in tobacco and in sprout inhibition in potato, onion, and garlic was substantially greater than the efficacy in the absence of the transition metal ion or its salt.It was discovered that the presence of a transition metal ion or a salt thereof was the source of the greater effectiveness of maleic hydrazide in suppressing suckers in tobacco, and in inhibiting sprouting in potato, onion, garlic, and this was considered surprising.
Claims
1. A composition with low toxicity comprising: a. at least one compound selected from a dicarboxylic acid hydrazide; and b. at least one transition metal ion or salt thereof.
2. The composition according to claim 1, wherein the levels of hydrazine in said formulation are less than or equal to 1 ppm.
3. The composition according to claim 1, wherein said transition metal ion is at least one selected from copper, iron, zinc, cobalt, nickel, silver, vanadium, chromium, manganese, mercury, scandium, titanium, tungsten, cadmium, platinum, rhodium, palladium, molybdenum, osmium, ruthenium, zirconium, and gold.
4. The composition according to claim 1, wherein said dicarboxylic acid hydrazide is at least one selected from maleic hydrazide, citric hydrazide, oxalic hydrazide, succinic hydrazide, malonic hydrazide, adipic hydrazide, italic hydrazide, and terephthalic hydrazide.
5. The composition according to claim 3, wherein said transition metal ion is incorporated into the composition in the form of a metal salt or in elemental form.
6. The composition according to claim 1, wherein said dicarboxylic acid hydrazide is maleic hydrazide and said transition metal ion is selected from copper, nickel, iron or a combination thereof.
7. The composition according to claim 1, wherein said composition is a solid or liquid composition selected from a powder, a powder suspended in water, a non-aqueous solution, a dry fluid, a liquid fluid, a true liquid, an emulsifiable concentrate, a fine powder, a wettable powder, a suspension, a soluble concentrate, a water-soluble granule, a water-dispersible granule, or a fluid suspension.
8. A composition with low toxicity comprising: a. at least one compound selected from a dicarboxylic acid hydrazide; and b. at least one transition metal ion or salt thereof, wherein the composition is substantially free of hydrazine.
9. The composition according to claim 9, wherein the levels of hydrazine in the composition are less than or equal to 1 ppm.
10. The method according to claim 9, wherein said dicarboxylic acid hydrazide is preferably maleic hydrazide and said transition metal ion is selected from copper, nickel, iron or a combination thereof.
11. A composition with low toxicity comprising: a. at least one compound selected from maleic hydrazide and b. at least one transition metal ion.
12. The formulation according to claim 9, wherein the levels of hydrazine in said composition are less than or equal to 1 ppm.
13. The composition according to claim 9, wherein the transition metal ion is selected from copper, nickel, manganese, iron, zinc or a combination thereof.
14. The composition according to claim 10, wherein the transition metal ion is copper ions.
15. Use of transition metal ions to control or reduce hydrazine levels in a composition comprising at least one compound selected from dicarboxylic acid hydrazides. αζη / Ln / zznz / 3 / γΐΛΐ 16. The use according to claim 12, wherein the transition metal ions regulate the levels of hydrazine in said composition to below or equal to 1 ppm.
17. The use according to claim 12, wherein said dicarboxylic acid hydrazide is preferably maleic hydrazide and said transition metal ion is selected from copper, nickel, iron or a combination thereof.
18. A method for preparing a low-toxicity composition comprising: a. dissolving transition metal salts in water to obtain the desired concentration of metal ions in the solutions; b. adding technical dicarboxylic acid hydrazide to said solution to form a suspension; c. mixing, filtering, and drying said suspension.
19. The method according to claim 18, wherein a method for preparing a liquid composition comprises: combining water and transition metal ions; adding said water to the dicarboxylic acid hydrazide.
20. A method of treating a plant, seed and / or plant propagation material at a location by applying a low toxicity composition comprising: a. at least one compound selected from a dicarboxylic acid hydrazide and b. at least one transition metal ion.
21. The method according to claim 20, wherein said dicarboxylic acid hydrazide is preferably maleic hydrazide and said transition metal ion is selected from copper, nickel, iron or a combination thereof.
22. The method according to claim 20, wherein the application is a seed treatment, applied before or after emergence.
23. According to any of the preceding claims, the amount of transition metal ions is less than, or approximately, 1000 ppm.
24. According to any of the preceding claims, the amount of transition metal ions is less than, or approximately, 125 ppm.
25. According to any of the preceding claims, the amount of transition metal ions is less than, or approximately, 2 ppm.
26. According to any of the preceding claims, the amount of transition metal ions is less than, or approximately, 1 ppm.
27. In accordance with any of the preceding claims, wherein the composition further comprises at least one acceptable agrochemical excipient.
28. According to any of the preceding claims, said composition is an anti-budding agent, a growth regulator and / or a pest control agent.