Novel bio-based ester amide mixtures and their use as solvents

Abstract

This invention relates to a novel bio-based esteramide mixture and its use as a solvent, and more particularly as a polar aprotic solvent, for example, for dissolving agricultural surfactants in agricultural formulations.

Description

[0001] This application claims priority to European application filed on 22 November 2023 under No. 23307027.5, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0002] This invention relates to a novel bio-based esteramide mixture and its use as a solvent, and more particularly as a polar aprotic solvent, for example, for dissolving agricultural surfactants in agricultural formulations. Background Technology

[0003] Industrial applications use many chemical compounds as solvents, for example, in the preparation of chemicals and materials, in the formulation of chemical compounds, or for surface treatment. Solvents are also used to formulate agricultural compounds, particularly phytosanitary agents (fertilizers, pesticides, etc.), which are, for example, in the form of emulsifiable concentrates (ECs) intended for farmers to dilute in water before application to fields.

[0004] The agricultural industry seeks to achieve the highest possible concentration of one or more agrochemical active compounds in corresponding formulations. This is because high concentrations of these compounds allow for reduced application volumes, thus saving on the amount of adjuvant material used, as well as in packaging and logistics. Therefore, highly concentrated, stable formulations and co-formulations with environmentally friendly adjuvants are of interest.

[0005] For agrochemical active compounds with low or relatively low water solubility, the preparation of concentrated liquid formulations using appropriate solvents is of particular interest. These concentrated liquid formulations are in the form of emulsifiable concentrates (EC), emulsions in water (EW), microemulsions (ME), suspensions (SE), oil dispersions (OD), and dispersible concentrates (DC). Further details regarding the definitions of these formulations can be found in the "Guidance document for the generation of data on the physical, chemical and technical properties of plant protection products, pursuant to Regulation (EC) 1107 / 2009 of the European Parliament and the Council on the placement of plant protection products on the market."

[0006] These concentrated formulations of agricultural compounds are typically diluted before agricultural use. Dilution by farmers usually involves mixing the agricultural chemical formulation with water.

[0007] Furthermore, certain solid agrochemical active compounds are often difficult to formulate. For some agrochemical compounds, it is difficult to produce concentrated formulations that are easily diluted by farmers, stable, and without substantial drawbacks (actual or perceived drawbacks) in terms of safety, toxicity, and / or ecotoxicity. For some agrochemical compounds, it is difficult to formulate at relatively high concentrations with sufficient stability. In particular, it is necessary to avoid the formation of crystals, especially at low temperatures and / or during dilution and / or during storage of the composition, particularly at low temperatures. Crystals can have adverse effects, especially clogging filters used for spreading and diluting the composition, clogging spray devices, reducing the overall activity of the formulation, creating unnecessary problems with waste management procedures for crystal removal, and / or causing poor distribution of one or more agrochemical materials in the field.

[0008] Therefore, the agrochemical industry is constantly seeking new solvents and solvent compositions with properties satisfactory for agricultural applications, such as good solubility for a wide range of agricultural compounds. Furthermore, the cost of solvent compositions should generally be moderate, and preferably they should have favorable toxicological and / or ecotoxicological characteristics, particularly low toxicity and / or low hazard potential, and / or low volatility (low VOCs - volatile organic compounds) and / or advantageously high biodegradability and / or renewability.

[0009] In the field of emulsifiable concentrate (EC) formulations, there is a need for polar aprotic solvents suitable for dissolving certain key active ingredients at high concentrations. N-methyl-2-pyrrolidone (NMP) or N,N-dimethylacetamide are very common polar aprotic solvents that can be used in such applications. However, due to their unfavorable toxicological characteristics, they are no longer used, and alternatives are being sought.

[0010] US 8,735,324 relates to the use of esteramide compounds as solvents.

[0011] One common esteramide compound used as a solvent is Rhodiasolv® PolarClean, which is methyl 5-(dimethylamino)-2-methyl-5-oxovalerate (C9H 17 NO3 (CAS No. 1174627-68-9) exhibits good solubility and good toxicity / ecotoxicity characteristics. However, this compound is not of biological origin, and molecules with improved solubility performance compared to some other compounds are still needed.

[0012] Unbound by any theory, it is believed that the presence of the ester functional group in the PolarClean solvent plays a key role in the molecule's excellent toxicity and ecotoxicity characteristics, thus acting as a "detoxifying" component. Conversely, and as mentioned above, for example, N,N-dimethylacetamide, lacking such an ester functional group, is a well-known reproductive toxicant.

[0013] Therefore, the object of the present invention is to provide a polar aprotic solvent of biological origin that exhibits improved solubility for a wide range of agrochemically active compounds. Summary of the Invention

[0014] This invention relates to a mixture comprising a compound having structure (IIIa) and a compound having structure (IIIb), and optionally a diamide compound having formula and structure (IIIc):

[0015]

[0016] And optionally diester compounds having formula (II):

[0017]

[0018] This ester-amide mixture of the present invention can be synthesized by amidation of dimethyl 2-methylsuccinate (DMMS) having formula (II). DMMS can be obtained by hydrogenation of dimethyl itaconic acid, which in turn can be obtained by esterification of itaconic acid with methanol.

[0019] Therefore, in another aspect, the present invention relates to a method for manufacturing the new esteramide mixture, the method comprising at least one of the steps described above.

[0020] In another aspect, the present invention relates to the use of this novel esteramide mixture as a solvent, for example, for dissolving agricultural surfactants in agricultural formulations. The solvent of the present invention (which is novel) has a structure very similar to PolarClean; however, it exhibits the following advantages:

[0021] 1. The solvent can be 100% bio-based, which helps reduce the overall CO2 footprint of formulations based on the solvent.

[0022] 2. Importantly, despite having a structure similar to PolarClean, this solvent exhibits improved solubility for several active ingredients, particularly azoxystrobin, difenoconazole, and oxadiazon.

[0023] Preferred embodiments of these aspects of the invention are set forth in the following description and the appended claims. Detailed Implementation

[0024] The following definitions are relevant to embodiments of the present invention.

[0025] The term “comprising” should be interpreted as encompassing all specifically mentioned features as well as optional, additional, or unspecified features, while the term “composed of” includes only those features as specified. Therefore, “comprising” as a limitation includes the preparations specified by “composed of”.

[0026] Unless the context clearly indicates otherwise, as used herein, the singular forms “a / an” and “the” include both the singular and plural indicators. For example, “a pesticide” means one or more pesticides.

[0027] As used herein, the term "solvent" refers to a compound that is a liquid at the operating temperature (preferably room temperature) and that helps dissolve solid substances or helps prevent / delay the solidification or crystallization of substances from their dissolved form.

[0028] As used in this article, the term "room temperature" refers to a temperature between 20°C and 30°C, typically 25°C.

[0029] Non-limiting examples of the term "pesticide" include insecticides, fungicides, herbicides, acaricides, algaecides, molluscicides, rodenticides, nematicides, biocides, and miticides. Specific examples of pesticides can be found in the book "Sittig's handbook of Pesticides and Agricultural Chemicals," 2nd edition, William Andrew Publishing, 2015.

[0030] As used herein, the term "nitrogen fertilizer stabilizer" refers to an agent that prevents or slows down the biodegradation kinetics of fertilizers. Non-limiting examples include urease inhibitors or nitrification inhibitors such as NBPT (N-(n-butyl)thiophosphoric acid triamine), DCD (dicyandiamide), and NPPT (N-(n-propyl)thiophosphoric acid triamine). Nitrification inhibitors delay the bacterial oxidation of ammonium ions in fertilizers by inhibiting the activity of *Nitrosomonas* bacteria in the soil, which convert ammonium to nitrite. Urease inhibitors inhibit the conversion of urea to ammonia and CO2. Fertilizers containing fertilizer stabilizers are often referred to as slow-release or controlled-release fertilizers or efficiency-enhancing fertilizers (EEF). Non-limiting examples of nitration inhibitors include DCD, DMPP (3,4-dimethylpyrazole phosphate), nitrapyrin (2-chloro-6-(trichloromethyl)pyridine), TU (thiourea), MT (1-mercapto-1,2,4-triazole), AM (2-amino-4-chloro-6-methylpyrimidine), ASU (1-amido-2-thiourea), TZ (1H-1,2,4-triazole), and 3,4-dimethylpyrazole succinate (DMPSA). Non-limiting examples of urease inhibitors include NBPT, NPPT, and CNPT (N-cyclohexylphosphotriamine).

[0031] As used herein, the term "formulation" refers to a composition comprising at least the mixture of the present invention and another ingredient / compound. The composition may be homogeneous (i.e., a solution) or heterogeneous (i.e., a dispersion, emulsion, suspension, or emulsion).

[0032] The term "% w / v" refers to the weight of the corresponding ingredient based on the total volume of the preparation.

[0033] The following further defines embodiments and preferred embodiments according to the present invention. Preferred embodiments are preferred individually or in combination. Furthermore, it should be understood that the following preferred embodiments refer to all aspects of the invention, namely mixtures, methods, formulations, and uses of the mixtures.

[0034] In one embodiment, the present invention relates to a mixture comprising compounds having structures (IIIa) and (IIIb), since these compounds are synthesized having the formula C8H 15The ester amide compound of NO3 is typically obtained as an accompanying isomer. The two isomers are obtained from diester precursor (II) according to a parallel reaction process, with (IIIa) being the major isomer and (IIIb) the minor isomer. The ratio of these isomers will depend on several parameters, particularly the temperature used during the amidation reaction. In some embodiments, the mixture may additionally contain a diamide compound having structure (IIIc), as this compound can also be generated as a byproduct during the synthesis of the ester amide of the present invention. In some embodiments, the mixture may additionally contain a diester precursor having structure (II), which is used for the synthesis of the ester amide of the formula C8H 15 The esteramide compounds of NO3 are produced through an amidation process. The residual amounts of diamide (IIIc) and diester (II) in the mixture are interrelated because diamide (IIIc) is a byproduct formed by the successive amidation side reactions of esteramides (IIIa) and / or (IIIb). Therefore, if diester (II) is not completely converted to esteramides (IIIa) / (IIIb), the amount of diamide (IIIc) will be limited, while residual diester (II) will be present in the mixture. Conversely, if diester (II) is almost completely converted, resulting in a very limited amount of (II) in the mixture, diamide (IIIc) will be present in a higher amount.

[0035] The above mixture typically contains 75 to 95 wt% of ester amide (IIIa), 5 to 15 wt% of ester amide (IIIb), 0 to 8 wt% of diester precursor (II), and 0 to 8 wt% of diamide (IIIc).

[0036] The present invention also relates to a method for manufacturing the ester-amide mixture of the present invention, the method comprising an amidation step of dimethyl 2-methylsuccinate (DMMS) (II). The amidation uses dimethylamine (DMA) as a reactant and is preferably catalyzed by a strong base (e.g., an alkali metal alkoxide, alkali metal amide, or alkali metal hydroxide). Preferred examples of catalysts are: sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, sodium amino, lithium amino, potassium amino, lithium diisopropylamino, sodium diisopropylamino, sodium bis(trimethylsilyl)amino, potassium bis(trimethylsilyl)amino, sodium hydroxide, lithium hydroxide, and potassium hydroxide. The amidation reaction is preferably catalyzed by sodium methoxide (MeONa), as described in US 8,735,324 mentioned above.

[0037] The amidation reaction is preferably carried out without any solvent by directly condensing the required amount of DMA gas into the diester precursor (II) at a low temperature (e.g., between 0°C and 10°C); or alternatively, a solvent may be used for the reaction. In this case, methanol, ethanol, isopropanol, THF, Me-THF, etc., may be mentioned as preferred solvents.

[0038] The DMA:(II) molar ratio can range from 0.8:1 to 2:1, and a stoichiometric ratio is generally preferred. The amidation reaction is typically carried out at atmospheric pressure (1 atm, but can also be carried out in an autoclave at higher pressures, such as up to 10 bar. The reaction is preferably carried out at a temperature between 25°C and 80°C, more preferably between 40°C and 60°C. The amount of catalyst used in the reaction is preferably between 0.5% and 15 mol% relative to the diester precursor (II), and more preferably between 2% and 10 mol%. During the reaction, an equimolar amount of methanol is formed as a byproduct, which can be separated and utilized later in the process.

[0039] In a preferred embodiment, the method of the present invention includes an additional step of synthesizing DMMS(II) by hydrogenation of dimethyl itaconic acid (DMI). This reaction is preferably a standard catalytic hydrogenation, preferably using a noble metal supported solid catalyst, such as a catalyst based on Ni, Pd, Pt, Ru, Rh, Cu, or Ir. Raney-type catalysts are also suitable for this reaction, and Raney nickel or Raney cobalt can be mentioned as examples. Preferred catalysts for this reaction are: Pd / C, Ru / C, Pd / Al₂O₃, Ru / Al₂O₃, and Raney nickel. A particularly preferred catalyst is Pd / C. The reaction is preferably carried out without any solvent, but alternatively, it can be carried out in the presence of an additional solvent. In this case, alcohols are particularly suitable for this hydrogenation reaction, and methanol, ethanol, isopropanol, tert-butanol, etc., can be mentioned. Alternatively, THF and Me-THF can also be suitable solvents. The reaction is preferably carried out in a hydrogen atmosphere, preferably in an autoclave at a pressure ranging from 2 to 50 bar, more preferably from 5 to 15 bar. The reaction temperature is preferably between 30°C and 150°C, more preferably between 40°C and 90°C.

[0040] In a preferred embodiment, the method of the present invention includes an additional step of synthesizing dimethyl itaconic acid (DMI) by esterification of itaconic acid (IA) with methanol, which is preferably catalyzed using a standard acid, preferably methanesulfonic acid, and / or carried out in the presence of a polymerization inhibitor (preferably hydroquinone). Other suitable alternative catalysts include other Bronsted acids such as sulfuric acid (H₂SO₄), p-toluenesulfonic acid (APTS), camphorsulfonic acid, trifluoromethanesulfonic acid, HCl, HBr, HI, etc. Solid heterogeneous acid catalysts are also suitable for this reaction, and preferred catalysts include Amberlyst resins, acidic zeolites, Nafion, Aquivion, etc. The esterification reaction is preferably carried out in the absence of an additional solvent, but alternatively, a solvent may be used during the reaction. Preferred solvents are those capable of forming an azeotrope with the water co-generated during the reaction, thus facilitating the removal of water from the reaction medium and thereby shifting the reaction equilibrium toward the formation of the ester product. The anhydrous solvent can then be recycled back to the reaction vessel after decantation using, for example, a so-called Dean-Stark device. Preferred solvents include, for example, toluene, xylene, cyclohexane, methylcyclohexane, anisole, etc. When carried out in the absence of an additional solvent, methanol is preferably added gradually to the reaction mixture in a fed-batch manner. In this case, under these reaction conditions, a portion of the added methanol, along with water, is flash-distilled from the reaction medium, thereby helping to shift the reaction equilibrium. The methanol and water can then be separated by distillation, and the unreacted methanol can be recycled back to the esterification medium. The preferred range of esterification reaction temperature is between 60°C and 130°C, more preferably between 90°C and 120°C. The reaction can be carried out at 1 atm, but alternatively, a slight vacuum can be used to assist in dehydration to improve reaction conversion. In this case, the pressure range can be between 200 mbar and 1 atm. Since itaconic acid and its esters are monomers, polymerization inhibitors are preferably used during the reaction to avoid polymerization side reactions. Examples of preferred polymerization inhibitors include hydroquinone (HQ), p-methoxyphenol (PMP), 4-tert-butylcatechol (TBC), phenothiazine (PTZ), etc. In this case, HQ and PMP are particularly preferred polymerization inhibitors.

[0041] The methods described above typically produce a mixture of compounds having structures (IIIa) and (IIIb) and optionally compounds having structures (IIIc) and / or (II), with the dominant substance typically being a compound having structure (IIIa).

[0042] The method described in conjunction with several preferred embodiments of the present invention is illustrated in the appendix. Figure 1In the study, compound (I) is DMI and compound (II) is DMMS, and the starting compound is itaconic acid (IA).

[0043] The method according to a preferred embodiment of the present invention includes the following steps:

[0044] 1. Synthesis of DMI (I) via esterification of itaconic acid (IA) with methanol;

[0045] 2. Synthesis of DMMS (II) by hydrogenation of DMI (I); and

[0046] 3. Amide reaction of DMMS (II) with DMA.

[0047] Preferably, the itaconic acid used in the method of the present invention is a bio-based structural unit produced by fermentation.

[0048] In yet another embodiment, the present invention relates to the use of the above-mentioned esteramide mixture as a solvent, for example, in agricultural formulations.

[0049] The use of the esteramide mixture of the present invention as a solvent also includes its use as a co-solvent and / or as a crystallization inhibitor. Use as a co-solvent means that the esteramide mixture is used in combination with at least one other solvent. The esteramide mixture can also act as a crystallization inhibitor, for example in emulsifiable concentrates in which the agriculturally active compound is present in a highly concentrated form, and then diluted by farmers in water for application to the field.

[0050] This ester-amide mixture advantageously exhibits not only good to excellent solubility properties, but also preferably very good safety and sustainability characteristics, wherein it has no hazard classification or very low hazard classification and no or very low ecotoxicity, and is also bio-based.

[0051] Therefore, this ester-amide mixture can generally be used as a substitute for toxic solvents such as N-methyl-2-pyrrolidone (NMP) or as a substitute for other polar and eco-friendly solvents such as NBP (N-butyl-2-pyrrolidone), Rhodiasolv® PolarClean, N,N-dimethyllactic acid and Rhodiasolv® ADMA 10.

[0052] In another aspect, the present invention relates to an agricultural formulation (or agricultural chemical formulation) comprising an agriculturally active compound and an ester amide mixture of the present invention, wherein the agriculturally active compound as described above may be used.

[0053] The agricultural formulation of the present invention may comprise:

[0054] a) At least one agronomic active compound (especially only one agronomic active compound, or a combination of different agronomic active compounds);

[0055] b) Mixtures of esteramides used as solvents or co-solvents;

[0056] c) Optionally at least one emulsifier and / or a surfactant; and

[0057] d) Optional ground water.

[0058] As used herein, the term "agricultural active compound" refers specifically to an active ingredient used in agricultural practices, including cultivating soil for crop growth. However, the use of agricultural active compounds is not limited to application to crops. Agricultural active compounds (or materials) can be applied to any surface, for example, for cleaning or to aid or inhibit the growth of living organisms. Other non-crop applications include, but are not limited to, application to turf and ornamental plants, as well as application to railway weeds.

[0059] Agricultural active compounds are typically products in pure or highly concentrated form.

[0060] The agricultural active compounds suitable for use in this invention are preferably selected from the group consisting of: pest control agents, biological pest control agents, fertilizers, fertilizer stabilizers, nutrients, biostimulants, plant growth regulators, natural plant defense enhancers, inoculants, and mixtures thereof.

[0061] Suitable pest control agents for use in this invention include herbicides, insecticides, acaricides, fungicides, algaecides, molluscicides, miticides, nematicides, biocides, and rodenticides, as well as mixtures thereof.

[0062] Non-limiting examples of fungicides suitable for use in this invention include: azoles, such as prothioconazole, flutriafol, difenoconazole, propiconazole, cyproconazole, and tebuconazole; acarbamates, such as pyraclostrobin, azoxystrobin, pyraclostrobin, fluazinam, and pyraclostrobin; and succinate dehydrogenase inhibitors (SDHI) (carboxamides), such as chlorofluorobifenpyroxen, fluopyram, benzo[a]fluorocyclohexane, and fluopyram; and mixtures thereof.

[0063] Particularly good results were obtained with azoxystrobin, difenoconazole and oxadiazon (see examples).

[0064] Agricultural active compounds at 20°C and atmospheric pressure (i.e., 1.013 x 10⁻⁶) 5 It can be water-insoluble under (Pa) conditions.

[0065] Specifically, the agricultural active compound is effective at 20°C and atmospheric pressure (i.e., 1.013 x 10⁻⁶). 5It is soluble in water up to 100 g / L, usually up to 20 g / L, noteworthyly up to 5 g / L, for example up to 1 g / L and even up to 0.2 g / L.

[0066] In another embodiment, the agricultural formulation is a fertilizer formulation, preferably an efficiency-enhancing fertilizer formulation, which contains fertilizer and / or fertilizer stabilizer, particularly nitrogen fertilizer and / or nitrogen fertilizer stabilizer and / or urease inhibitor and / or nitrification inhibitor.

[0067] Fertilizers and / or fertilizer stabilizers, especially nitrogen fertilizers and / or nitrogen fertilizer stabilizers and / or urease inhibitors and / or nitrification inhibitors, may be N-(n-butyl)thiophosphate triamide (NBPT) and / or dicyandiamide (DCD).

[0068] In another embodiment, the fertilizer formulation further comprises at least one biostimulant, a plant growth regulator, a natural plant defense enhancer, and / or an inoculant.

[0069] In another embodiment, the fertilizer formulation further comprises at least one pest control agent, such as a herbicide, insecticide, fungicide, acaricide, algaecide, molluscicide, miticide, nematicide, biocide, or rodenticide (e.g., rodenticide).

[0070] Typically, the amount of one or more agronomic active compounds in the agricultural formulations of the present invention ranges from 0.01% to 90% by weight, preferably 0.1% to 90% by weight, more preferably 0.1% to 80% by weight, even more preferably 0.5% to 70% by weight, better still 1% to 65% by weight, particularly 5% to 60% by weight, and for example 10% to 60% by weight.

[0071] According to a specific embodiment of the present invention (concentrated formulation), the total content of one or more agronomic active compounds in the agricultural formulation ranges from 5% to 90% by weight, preferably from 5% to 70% by weight, more preferably from 5% to 60% by weight, and particularly from 10% to 60% by weight, relative to the total weight of the agricultural formulation.

[0072] According to another specific embodiment of the invention (diluted formulation), the total content of one or more agronomic active compounds in the agricultural formulation ranges from 0.01% to 3% by weight, preferably from 0.05% to 2% by weight, and more preferably from 0.1% to 1% by weight, relative to the total weight of the agricultural formulation.

[0073] Typically, the ester-amide mixture accounts for 10% to 99.9% by weight, preferably 10% to 99% by weight, more preferably 20% to 95% by weight, particularly 30% to 90% by weight, for example 30% to 80% by weight, relative to the total weight of the agricultural chemical formulation.

[0074] Several agriculturally active compounds can be combined in the agricultural formulation of the present invention.

[0075] The agricultural formulations according to the present invention may contain at least one biostimulant.

[0076] The term "biostimulant" is preferably intended to mean a compound that can enhance metabolic or physiological processes such as respiration, photosynthesis, nucleic acid uptake, ion uptake, nutrient delivery, or combinations thereof.

[0077] Typically, this refers to substances or microorganisms that, when applied to seeds, plants, or the rhizosphere, can stimulate natural processes to enhance or benefit nutrient uptake, nutrient utilization efficiency, tolerance to abiotic stresses, or crop quality and yield.

[0078] Non-limiting examples of biostimulants include seaweed extracts (e.g., *Ascophyllum nodosum*), humic acids (e.g., potassium humate), fulvic acid, inositol, glycine, and combinations thereof.

[0079] The agricultural formulations according to the present invention may contain at least one plant growth regulator.

[0080] Plant growth regulators refer to active ingredients used to influence the growth characteristics of plants. Examples of plant growth regulators that can be used in this invention include, but are not limited to: 1-naphthaleneacetic acid, 1-naphthaleneacetic acid salt, 1-naphthol, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, 2,4-DEP, 2,3,5-triiodobenzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2-naphthoxyacetic acid, sodium salt of 2-naphthoxyacetic acid, 3-chloro-4-hydroxyphenylacetic acid, 3-indoleacetic acid, 4-biphenylacetic acid, 4-chlorophenoxyacetic acid (4-CPA), 4-hydroxyphenylacetic acid, 6-benzylaminopurine, auxindole, α-naphthaleneacetic acid K-salt, β-naphthoxyacetic acid, dicamba, 2,4-dichlorpropionic acid, 2,4,5-fenopropionic acid, indole-3-acetic acid (IAA), indole-3-acetyl-DL-aspartic acid, indole-3-acetic acid... Acyl-DL-tryptophan, indole-3-acetyl-L-alanine, indole-3-acetyl-L-valine, indole-3-butyric acid (IBA), indole-3-butyric acid K-salt, indole-3-propionic acid; α-naphthaleneacetic acid, indole-3-acetic acid methyl ester, naphthylacetamide, naphthaleneacetic acid (NAA), phenylacetic acid, picaridin, potassium naphthenate, sodium naphthenate, 4-hydroxyphenylethanol, 4-CPPU, 6-benzylaminopurine (BA) 6-(Y,Y-dimethylallylamino)purine (2iP), 2-iP-HC1, adenine, adenine hemisulfate, benzyladenine, kinetin, meta-topolin, N6-benzoyladenine, N-benzyl-9-(2-tetrahydropyranyl)adenine (BPA), N-(2-chloro-4-pyridyl)-N-phenylurea, gibberellin (GA3), gibberellin, gibberellin A4 + A7 (GA n), ethylene, and abscisic acid.

[0081] The agricultural formulations according to the present invention may optionally contain at least one emulsifier.

[0082] Emulsifiers are reagents designed to promote emulsification and / or stabilization of emulsions (over time and / or at temperature) after a formulation has been placed in the presence of water, for example by preventing phase separation.

[0083] Typically, the total amount of one or more emulsifiers in the agricultural formulation according to the invention ranges from 0.05% to 40% by weight, preferably from 0.1% to 35% by weight, more preferably from 0.5% to 30% by weight, particularly from 1% to 25% by weight, for example from 1% to 5% by weight, relative to the total weight of the agricultural formulation.

[0084] Typically, the agricultural chemical formulations according to the present invention further comprise at least one surfactant.

[0085] Advantageously, the surfactants that can be used in this invention are selected from anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, and mixtures thereof.

[0086] Preferably, the surfactant is selected from anionic surfactants, nonionic surfactants, and mixtures thereof.

[0087] More preferably, the surfactant is selected from anionic surfactants, polyalkoxylated nonionic surfactants, and mixtures thereof.

[0088] The emulsifiers and surfactants that can be used are different from one or more agricultural active compounds.

[0089] As examples of anionic surfactants, the following can be mentioned without any intended limitations:

[0090] - Alkyl sulfonic acids, aryl sulfonic acids, which may optionally be substituted with one or more hydrocarbon groups, and whose acid functional groups are partially or completely salted, such as C8-C 50 Alkyl sulfonic acids, more specifically C8-C 30 Preferably C 10 -C 22 Alkyl sulfonic acids, benzene sulfonic acids, naphthalene sulfonic acids, which are bounded by one to three C1-C2 groups. 30 Preferably C4-C 16 Alkyl and / or C2-C 30 Preferably C4-C 16 Alkenyl substitution,

[0091] - A monoester or diester of sulfosuccinic acid, wherein the straight-chain or branched alkyl portion is optionally substituted with one or more straight-chain or branched C2-C4 hydroxylated and / or alkoxylated (preferably ethoxylated, propoxylated, or ethpropoxylated) groups.

[0092] - Phosphate esters, more particularly selected from those comprising at least one straight-chain or branched, saturated, unsaturated, or aromatic hydrocarbon group containing 8 to 40 carbon atoms, preferably 10 to 30 carbon atoms, optionally substituted with at least one alkoxylated (ethoxylated, propoxylated, ethpropoxylated) group. Furthermore, they comprise at least one monoesterified or diesterized phosphate ester group, such that they may have one or two free or partially or fully salted groups. Preferred phosphate esters are of the type of monoester and diester of: phosphoric acid and alkoxylated (ethoxylated and / or propoxylated) mono-, di-, or tri-styrylphenol, or alkoxylated (ethoxylated and / or propoxylated) mono-, di-, or tri-alkylphenol, optionally substituted with one to four alkyl groups; phosphoric acid and alkoxylated (ethoxylated or propoxylated) C8-C 30 Preferably C 10 -C22 Alcohols; phosphoric acid and non-alkoxylated C8-C 22 Preferably C 10 -C 22 alcohol,

[0093] - A sulfate ester obtained from a saturated or unsaturated or aromatic alcohol, optionally substituted with one or more alkoxylated (ethoxylated, propoxylated, ethpropoxylated) groups, wherein the sulfate functional group is present in the form of a free acid or is partially or completely neutralized. As an example, more particularly examples of saturated or unsaturated C8-C... 20 Sulfates obtained from alcohols, which may contain 1 to 8 alkoxylation (ethoxylation, propoxylation, ethpropoxylation) units; sulfates obtained from polyalkoxylated phenols, which are oxidized by 1 to 3 saturated or unsaturated C2-C bonds. 30 Hydrocarbon substitution, wherein the number of alkoxylation units is between 2 and 40; sulfate esters obtained from polyalkoxylated mono-, di-, or tri-styrylphenols (where the number of alkoxylation units varies from 2 to 40).

[0094] Anionic surfactants can be in acidic form (they are potentially anionic) or in partially or fully salted form with a counterion. The counterion can be an alkali metal (such as sodium or potassium), an alkaline earth metal (such as calcium), or even have the formula N(R)4. + The ammonium ion, wherein the R groups are the same or different, representing a hydrogen atom or a C1-C4 alkyl group optionally substituted with an oxygen atom.

[0095] As examples of nonionic surfactants, the following can be mentioned without any intended limitations:

[0096] - Polyalkoxylated (ethoxylated, propoxylated, ethpropoxylated) phenol, which is bonded by at least one C4-C 20 Preferably C4-C 12The alkyl group is substituted or substituted with at least one alkylaryl group, wherein the alkyl portion of the alkylaryl group is C1-C6 alkyl. More specifically, the total number of alkoxylated units is between 2 and 100. As examples, polyalkoxylated mono-, di-, or tri-(phenylethyl)phenol, or polyalkoxylated nonylphenol, may be mentioned. Among ethoxylated and / or propoxylated, sulfated and / or phosphorylated di- or tri-styrylphenols, references may be made to ethoxylated di-(phenyl-1-ethyl)phenol containing 10 oxoethylidene units; ethoxylated di-(phenyl-1-ethyl)phenol containing 7 oxoethylidene units; sulfated ethoxylated di-(phenyl-1-ethyl)phenol containing 7 oxoethylidene units; ethoxylated tri-(phenyl-1-ethyl)phenol containing 8 oxoethylidene units; ethoxylated tri-(phenyl-1-ethyl)phenol containing 16 oxoethylidene units; sulfated ethoxylated tri-(phenyl-1-ethyl)phenol containing 16 oxoethylidene units; ethoxylated tri-(phenyl-1-ethyl)phenol containing 20 oxoethylidene units; and phosphorylated ethoxylated tri-(phenyl-1-ethyl)phenol containing 16 oxoethylidene units.

[0097] - Polyalkoxylation (ethoxylation, propoxylation, ethpropoxylation) C6-C 22 Fatty acids or alcohols. The number of alkoxylation units is between 1 and 60. The term ethoxylated fatty acids includes both products obtained by ethoxylation of fatty acids with ethylene oxide and those obtained by esterification of fatty acids with polyethylene glycol.

[0098] - Polyalkoxylated (ethoxylated, propoxylated, ethpropoxylated) triglycerides of plant or animal origin. Therefore, this may include triglycerides derived from lard, tallow, ground nut oils, butter, cottonseed oil, linseed oil, olive oil, palm oil, grapeseed oil, fish oil, soybean oil, castor oil, rapeseed oil, coprah oil, and coconut oil, and the total number of alkoxylated units included therein is between 1 and 60. The term ethoxylated triglyceride refers to both products obtained by ethoxylation of triglycerides with ethylene oxide and products obtained by transesterification of triglycerides with polyethylene glycol.

[0099] - Dehydrated sorbitan esters, which may optionally be polyalkoxylated (ethoxylated, propoxylated, ethpropoxylated), and more particularly C 10 -C 20 Cyclic sorbitol esters of fatty acids such as lauric acid, stearic acid, or oleic acid, wherein the total number of alkoxylated units included therein is between 2 and 50.

[0100] Useful emulsifiers, particularly the following products, are all sold by the applicant:

[0101] - Soprophor® TSP / 724: A surfactant based on ethoxylated tristyrylphenol.

[0102] - Soprophor® 796 / P: A surfactant based on ethoxylated tristyrylphenol.

[0103] Soprophor® CY 8: A surfactant based on ethoxylated tristyrylphenol.

[0104] - Soprophor® BSU: A surfactant based on ethoxylated tristyrylphenol.

[0105] - Soprophor® S / 25: A surfactant based on ethoxylated tristyrylphenol.

[0106] - Soprophor® 3D33: A surfactant based on ethoxylated tristyrylphenol phosphate.

[0107] - Alkamuls® RC: A surfactant based on ethoxylated castor oil.

[0108] - Alkamuls® OR / 36: A surfactant based on ethoxylated castor oil.

[0109] - Alkamuls® VO2003: A surfactant based on ethoxylated castor oil.

[0110] - Alkamuls® OL40: A surfactant based on ethoxylated dehydrated sorbitan hexaoleate.

[0111] - Alkamuls® T / 20: A surfactant based on ethoxylated dehydrated sorbitol esters.

[0112] - Geronol® TBE724: A surfactant based on ethoxylated tristyrylphenol.

[0113] - Geronol® TEB25: A mixture of surfactants based on ethoxylated castor oil, calcium dodecylbenzenesulfonate, and alkoxylated polymers.

[0114] - Rhodacal® 60 / B: A surfactant based on dodecylbenzene sulfonate.

[0115] - Rhodacal® 60 / BE: A surfactant based on dodecylbenzene sulfonate.

[0116] Typically, the total amount of one or more surfactants in the agricultural formulation according to the invention ranges from 0.05% to 40% by weight relative to the total weight of the agricultural formulation, preferably from 0.1% to 35% by weight, more preferably from 0.5% to 30% by weight, particularly from 1% to 25% by weight, for example from 1% to 5% by weight.

[0117] Typically, the total amount of one or more anionic surfactants in the agricultural formulation according to the invention ranges from 0.05% to 40% by weight, preferably from 0.1% to 35% by weight, more preferably from 0.5% to 30% by weight, particularly from 1% to 25% by weight, for example from 1% to 5% by weight, relative to the total weight of the agricultural formulation.

[0118] Typically, the total amount of one or more nonionic surfactants, particularly one or more polyalkoxylated nonionic surfactants, in the agricultural formulations according to the invention ranges from 0.05% to 40% by weight, preferably from 0.1% to 35% by weight, more preferably from 0.5% to 30% by weight, particularly from 1% to 25% by weight, for example from 1% to 5% by weight, relative to the total weight of the agricultural formulation.

[0119] The agricultural formulations according to the present invention may further contain at least one co-solvent different from the ester amide mixture of the present invention.

[0120] The other solvent or co-solvent can typically be selected from:

[0121] - Straight-chain or branched, saturated or unsaturated aliphatic hydrocarbons that may contain halogen atoms, phosphorus atoms, sulfur atoms and / or nitrogen atoms and / or functional groups.

[0122] - A carbocyclic or heterocyclic hydrocarbon, either saturated, unsaturated, or aromatic, which may contain halogen atoms, phosphorus atoms, sulfur atoms, and / or nitrogen atoms and / or functional groups.

[0123] More specifically, this cosolvent is selected from:

[0124] - Alkanes, cycloalkanes and aromatic derivatives, such as paraffins with branched or straight chains like "white oil" or decahydronaphthalene; mono-, di- or trialkylbenzenes or naphthalenes, compounds sold under the name Solvesso® 100, 150, 200 standard and ND grade;

[0125] - Aliphatic, alicyclic, or aromatic monoesters, diesters, or trimers, such as alkyl esters of alkanonic acids like methyl oleate; benzyl esters of alkanonic acids; alkyl esters of benzoates; γ-butyrolactone; γ-valerolactone; caprolactone; esters of glycerol and citric acid; alkyl esters of salicylate; phthalates; dibenzoates; acetoacetates; glycol ether acetates, dipropylene glycol diacetates; lactates; fumarates, succinates, adipates, maleates; acetopropionic acid esters;

[0126] - Mono-, di-, or tri-alkyl phosphates, such as triethyl phosphate; tributyl phosphate; or tri-2-ethylhexyl phosphate;

[0127] - Aliphatic, alicyclic, or aromatic ketones, such as dialkyl ketones; benzyl ketones; fenestrate ketones; acetophenones; cyclohexanones; alkylcyclohexanones; isophorones; cyclopentanones.

[0128] - Aliphatic, alicyclic, or aromatic alcohols, such as diols; 2-ethylhexanol; cyclohexanol; benzyl alcohol; tetrahydrofurfuryl alcohol;

[0129] - Aliphatic, alicyclic, or aromatic ethers, such as ethers of glycols, notably ethylene glycol and propylene glycol, and their polymers; diphenyl ethers, diphenyl ethers of dipropylene glycol; monomethyl ethers or monobutyl ethers, monobutyl ethers of tripropylene glycol; alkoxyalkanols; dimethyl isosorbide;

[0130] - Fatty acids, such as linoleic acid, linolenic acid, and oleic acid;

[0131] - Carbonates, such as propylene carbonate or butylene carbonate;

[0132] - Amides, such as dimethylalkylamide, dimethyl-decanoamide; N-alkyl-pyrrolidone; dimethyl lactamide.

[0133] - Alkyl urea;

[0134] - Amines, such as alkanolamines and morpholines;

[0135] - Tetramethyl sulfone; sulfolane;

[0136] - Dimethyl sulfoxide;

[0137] - Halogenated alkanes or halogenated aromatic solvents, such as chloroalkanes or chlorobenzenes.

[0138] Crystallization inhibitors may also be present in agricultural formulations according to the present invention. Crystallization inhibitors may be the co-solvents mentioned above. Crystallization inhibitors may also be non-polyalkoxylated fatty alcohols or fatty acids (e.g., Alkamuls® OL700, a product sold by the applicant, may be mentioned), alkanolamides, or polymers.

[0139] The agricultural formulations according to the invention may further contain one or more additives different from the previously described ingredients, and these additives are preferably selected from viscosity modifiers, suspending agents, antifoaming agents and defoamers (especially silicone antifoaming agents and defoamers), anti-rebound agents, anti-leaching agents, penetration aids, inert fillers (especially mineral fillers), adhesives, diluents, antifreeze agents, stabilizers, dyes, emetics, adhesives (adhesion promoters), absorbents, dispersants, disintegrants, wetting agents, preservatives and / or antimicrobial agents.

[0140] Each additive may be present in the agricultural formulation according to the invention at an amount ranging from 0% to 20% by weight, preferably 0% to 10% by weight, relative to the total weight of the agricultural formulation. Each additive may, for example, be present in the agricultural formulation according to the invention at an amount ranging from 0.1% to 20% by weight, particularly 0.1% to 10% by weight, relative to the total weight of the formulation. Each additive may be present in the agricultural chemical formulation according to the invention at an amount preferably ranging from 0% to 5% by weight, notably 0.1% to 5% by weight, relative to the total weight of the formulation. Those skilled in the art will be able to select these optional additives and their amounts such that they do not impair the properties of the agricultural formulation of the invention.

[0141] Advantageously, the agricultural formulation according to the invention is effective at 20°C and atmospheric pressure (i.e., 1.013 × 10⁻⁶). 5 It is in liquid form at Pa, and can be in the form of a concentrate, diluted concentrate, or sprayable diluted form of one or more agricultural active compounds.

[0142] Different types of formulations can be used depending on one or more different agrochemical active compounds. The formulations that can be used depend on the physical form of the agrochemical active material (e.g., solid or liquid) and its physicochemical properties in the presence of other compounds (e.g., water or solvent).

[0143] For practical reasons (e.g., ease of handling), formulations in liquid form may be preferred. Depending on the physicochemical properties of one or more different agrochemically active compounds under consideration, formulations may be in the following forms: emulsifiable concentrate (EC), emulsion concentrate in water (EW), microemulsion (ME), suspension (SE), oil dispersion (OD), dispersible concentrate (DC), suspension concentrate (SC), capsule suspension (CS), soluble liquid (SL), and flowable concentrate for seed treatment (FS).

[0144] Preferably, the agricultural formulations according to the present invention are in the following forms: emulsifiable concentrate (EC), emulsion concentrate in water (EW), microemulsion (ME), suspension (SE), oil dispersion (OD), dispersible concentrate (DC), capsule suspension (CS), and soluble liquid (SL).

[0145] More preferably, the agricultural formulations according to the present invention are in the form of emulsifiable concentrates, aqueous emulsion concentrates, microemulsion concentrates, suspension emulsion concentrates, oil dispersion concentrates, or dispersible concentrates.

[0146] In a specific embodiment, the agricultural formulation according to the present invention is in the form of an emulsifiable concentrate (EC).

[0147] The agricultural formulations according to the invention are typically concentrated agrochemical formulations and are intended to be spread on cultivated or uncultivated fields, most often after dilution with water to obtain a diluted formulation. Dilution is usually carried out by the farm operator directly in a bucket (“bucket mix”), for example in a bucket of a device designed for spreading the formulation. This does not preclude the possibility of the farm operator adding other plant protection products such as fungicides, herbicides, pest control agents, insecticides, fertilizers, adjuvants, etc. Therefore, the formulation can be used to prepare a diluted formulation of one or more agrochemically active compounds by mixing at least one part by weight of the concentrated formulation with at least 10 parts, preferably less than 10,000 parts, of water. The dilution ratio and amount to be applied to the field typically depend on one or more agrochemically active compounds and the desired dosage for treating the field (which can be determined by the farm operator).

[0148] According to one embodiment of the present invention, the agricultural chemical formulation according to the present invention is water-based.

[0149] According to this embodiment, the water content of the agricultural preparation is preferably 5% to 99% by weight relative to the total weight of the agricultural preparation, more preferably 20% to 95% by weight, even more preferably 25% to 90% by weight, particularly 25% to 85% by weight, for example 25% to 70% by weight.

[0150] According to this embodiment, the pH range is preferably from 1 to 11, and particularly from 2.5 to 9.5.

[0151] The pH of the preparation can be adjusted to the desired value using alkalizing or acidifying agents. Among alkalizing agents, one or more alkalis can be used, such as ammonia, sodium hydroxide, or ethanolamine. For example, among acidifying agents, inorganic or organic acids, such as hydrochloric acid or phosphoric acid, can be mentioned.

[0152] According to specific embodiments of the invention, agricultural formulations may advantageously comprise:

[0153] a) At least one agronomic active compound (only one agronomic active compound or a combination of different agronomic active compounds) at 0.01% to 90% by weight, preferably 5% to 60% by weight, relative to the total weight of the agricultural formulation, and preferably at least one pest control agent.

[0154] b) A mixture of the compounds according to the invention, at 5% to 90% by weight, preferably 10% to 90% by weight, particularly 30% to 90% by weight, or for example 30% to 80% by weight, relative to the total weight of the agricultural preparation.

[0155] c) At least one of the co-solvents, comprising 0.1% to 40% by weight, preferably 1% to 30% by weight, relative to the total weight of the agricultural formulation.

[0156] d) At least one surfactant, comprising 0.05% to 40% by weight, preferably 0.1% to 35% by weight, more preferably 0.5% to 30% by weight, and particularly 1% to 25% by weight, for example 1% to 5% by weight, relative to the total weight of the agricultural formulation.

[0157] e) Water, at a weight of 5% to 90%, preferably 10% to 80%, and particularly 25% to 70%, relative to the total weight of the agricultural preparation.

[0158] Conventional methods known for preparing agricultural formulations can be implemented. This can be achieved by simply mixing the components.

[0159] The agricultural formulations according to the present invention can be used to kill or inhibit harmful organisms and / or remove unwanted plants and / or inhibit the growth of unwanted plants.

[0160] The agricultural formulations according to the invention can be diluted and applied in a conventional manner to at least one plant, an area adjacent to the plant, soil suitable for supporting plant growth, the roots of the plant, the leaves of the plant, and / or seeds suitable for growing the plant; for example, by watering (sprinkling), drip irrigation, spraying, and / or atomizing.

[0161] In addition to its use as a solvent, cosolvent, and / or crystallization inhibitor (particularly in agricultural formulations), the esteramide mixtures of the present invention can also be used as solvents in coating applications, membrane manufacturing, or solid-state batteries.

[0162] Furthermore, the ester-amide mixture of the present invention can be used in the recycling of polymers, especially chemically resistant polymers such as PVDF or PVDC (polyvinylidene chloride), and can also be used as a substitute for polar solvents such as NMP, DMF, DMSO, acetophenone and DMAc.

[0163] The ester-amide mixture of the present invention can also be used as a solvent for preparing condensation polymers in solution, especially polyimides or polyesters or polyamides or polyamide-imides, especially partially or fully aromatic condensation polymers such as aromatic polyamides (aromatic polyamides).

[0164] Furthermore, the ester-amide mixture of the present invention can be used as a cleaning solvent for cleaning equipment such as, for example, reactors, particularly polymerization reactors.

[0165] Because the esteramide mixtures of the present invention are advantageously eco-friendly solvents and preferably have good safety and sustainability characteristics, they can also be advantageously used as solvents in household care formulations for use in homes or public areas (hotels, offices, factories, etc.). They can be formulated for cleaning hard surfaces such as floors, furniture surfaces, and kitchen and bathroom fixtures or tableware. These formulations can also be used in industrial applications, for example, for degreasing manufactured products and / or for cleaning them.

[0166] If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with this specification to the extent that it may obscure the terminology, this specification shall prevail. Example

[0167] The reactions described below are always carried out under an inert argon atmosphere.

[0168] 1. Esterification of itaconic acid (IA) with methanol to obtain DMI

[0169] The reaction was carried out in a 1 L double-jacketed reactor equipped with a mechanical stirrer (with four tilting plow propellers) and baffles, a temperature probe and distillation equipment.

[0170] Add to the reactor:

[0171] -300 g of itaconic acid (2.31 mol).

[0172] -221.6 g of dry methanol (280 mL, 6.92 mol).

[0173] -260 mg of hydroquinone (for polymerization inhibition)

[0174] -6.6 g of methanesulfonic acid (69 mmol) was used as a catalyst.

[0175] The reaction mixture is allowed to be stirred at 400 rpm and the reaction is carried out at 100°C-110°C (reactant temperature), wherein additional amounts of methanol are added gradually in batches as methanol and water byproducts are flashed out during the reaction, thereby shifting the reaction equilibrium toward the completion of esterification.

[0176] Specifically, this was accomplished by regularly adding 666 g of methanol (841 mL, 20.8 mol) over 15 hours.

[0177] After a reaction time of 15 hours at 100°C-110°C, the container pressure was reduced to 600 mbar to achieve complete conversion toward diester.

[0178] The temperature was then lowered to 90°C, and 11 g of Na2CO3 (103.5 mmol) was added to the reactants at 1 atm for catalyst neutralization.

[0179] The mixture was allowed to be stirred at 90°C for 3 hours, and 1.32 g of methanesulfonic acid was introduced into the reaction mixture.

[0180] The product was then purified by vacuum distillation (at 120°C and 40 mbar pressure in a vessel) to obtain a clear liquid product.

[0181] 1 H NMR (CD3OD, 400 MHz) δ (ppm): 6.28 (s, 1H), 5.78 (s, 1H), 3.74 (s,3H), 3.67 (s, 3H), 3.37 (s, 2H).

[0182] 2. Catalytically hydrogenate DMI to DMMS (II).

[0183] In a 750 mL hydrogenation autoclave reactor equipped with a Rushton turbine and baffles, the following were added sequentially at room temperature:

[0184] -120 g of dimethyl itaconic acid (I) (0.76 mol, half).

[0185] -261.2 mg Pd / C (3%) (Chimet 1221 L, 50% moisture).

[0186] -120 g of dimethyl itaconic acid (I) (0.76 mol, the other half).

[0187] The autoclave was then sealed and purged three times with 10 bar nitrogen to reduce the oxygen content (without stirring).

[0188] Then purge the autoclave three times with 10 bar hydrogen gas (without stirring).

[0189] The mixture was then allowed to be stirred at 800 rpm (at a hydrogen pressure of 10 bar) and the temperature of the reactants was raised to 50°C.

[0190] Once the slurry is stirred, the hydrogenation reaction begins, accompanied by the consumption of hydrogen and the observation of exothermic reactions (the heat of hydrogenation is estimated to be about 27 kcal / mol).

[0191] The reaction conversion rate was tracked and monitored by hydrogen consumption, showing that hydrogenation was completed after 2 h00 reaction time (50°C, 10 bar).

[0192] The reaction mixture was then allowed to cool at room temperature under hydrogen pressure. The autoclave was then depressurized and the solid catalyst was filtered out using a filter (11 μm polypropylene membrane).

[0193] The product, which is a transparent, colorless liquid, is then obtained in quantitative yield and used as is in the next step.

[0194] 1 H NMR (CDCl3, 400 MHz) δ (ppm): 3.67 (s, 3H), 3.65 (s, 3H), 2.91-2.87(m, 1H), 2.70 (dd, 1H, J = 16.4 Hz, 8.1 Hz), 2.36 (dd, 1H, J = 16.4 Hz, 6.1Hz), 1.17 (d, 3H, J = 7.2 Hz).

[0195] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 175.57, 172.16, 51.80, 51.58, 37.30, 35.64, 16.90.

[0196] 3. Amidation of DMMS (II) to obtain compounds having structures IIIa and IIIb.

[0197] The reaction was carried out in a carefully dried container under an inert nitrogen atmosphere.

[0198] Unless otherwise stated, all reactants are used as is without any further purification.

[0199] Before use, the DMA solution in methanol was dried overnight on activated molecular sieve 4A (Karl-Fisher analysis confirmed that the residual water content after drying was less than 600 ppm).

[0200] Add the following to a 1 L double-jacketed reactor at room temperature, equipped with a mechanical stirrer (four-plow glass stirrer), baffles, a condenser maintained at 5°C, and a temperature probe:

[0201] -94.01 g (0.587 mol) of diester intermediate (II).

[0202] -458.2 g of DMA in methanol (2 M) (561.9 mL, 1.124 mol, 1.9 equivalents).

[0203] The mixture was then allowed to be stirred at 400 rpm, and 0.992 g of NaOMe (approximately 3 mol% relative to (II)) catalyst was added to the reaction mixture in one step.

[0204] The reaction mixture was then allowed to be stirred at 50°C (400 rpm), and the reaction progress was tracked over time by 1H NMR analysis.

[0205] After stirring at 50°C for 2 hours, the conversion level was approximately 9%.

[0206] The reaction mixture was then allowed to be stirred at 50°C for 16 hours, thereby allowing a conversion level of 35% to be achieved.

[0207] An additional 2.2 g of NaOMe catalyst (approximately 7 mol% relative to (II)) was added to the reaction mixture to accelerate the reaction kinetics.

[0208] The reaction mixture was then allowed to be stirred again at 50°C (400 rpm) for 24 hours.

[0209] At this stage, the conversion level reaches 93%, and excess DMA and methanol are distilled off from the vessel (reactants at 42°C, 300 mbar during distillation).

[0210] The alkaline catalyst contained in the crude product was then neutralized at room temperature by adding an aqueous solution of H3PO4 (85 wt%) to achieve a final pH of approximately 6.5 (measured at 25°C with a 10 wt% dilution in water).

[0211] The final product was then purified by vacuum distillation.

[0212] After distilling the residual water and methanol (from catalyst neutralization), the first fraction (bp 75°C, 2 mbar, 4.7 g) was obtained.

[0213] 1 1H NMR analysis showed that the fraction was mainly composed of starting material (DMMS).

[0214] The second fraction (bp 122°C, 2 mbar, 54.4 g) was then collected, which corresponded to the desired products (IIIa and IIIb).

[0215] At the end of distillation, approximately 37 g of solid material (high-boiling matter) remains in the distillation vessel.

[0216] For the purified product 1 1H NMR analysis showed that the product was a mixture of the following two isomers in the following amounts: (IIIa) = 87.1% and (IIIb) = 7.1%.

[0217] 1 ¹H NMR (CDCl₃, 500 MHz) δ (ppm) Major isomer (IIIa): 3.61 (s, 3H), 2.94 (brs, 3H), 2.94–2.85 (m, 1H), 2.85 (brs, 3H), 2.71 (dd, 1H, J = 16.6 Hz, 8.5 Hz), 2.26 (dd, 1H, J = 16.6 Hz, 5.0 Hz), 1.14 (d, 3H, J = 7.2 Hz).

[0218] 13 C NMR (CDCl3, 126 MHz) δ (ppm) Major isomers (IIIa): 176.9, 171.0, 51.9, 37.1, 36.8, 35.9, 35.5, 17.5.

[0219] 1 ¹H NMR (CDCl₃), 500 MHz) δ (ppm) Minor isomer (IIIb): 3.55 (s, 3H), 3.2–3.1 (m, 1H), 3.03 (brs, 3H), 2.85 (brs, 3H), 1.03 (d, 3H, J = 7.0 Hz), only non-overlapping signals are indicated here.

[0220] 13 C NMR (CDCl3, 126 MHz) δ (ppm) Minor isomers (IIIb): 175.3, 173.1, 51.6, 38.0, 37.2, 35.7, 32.3, 17.4.

[0221] 4. Solubility test of active ingredients.

[0222] Solubility tests were conducted, including evaluating the solubility of several key strategic fungicides at different concentrations and at room temperature (RT) and 0°C in the solvents of this invention.

[0223] The solution was monitored for one week to observe any active ingredient crystallization during the aging process.

[0224] Mixtures are prepared by dissolving active ingredients (or combinations thereof) at a specific concentration (g / L) in a solvent system (pure). Each active ingredient is weighed individually and added to the solvent system. The mixture is stirred at 60 rpm using a rotary drive at room temperature for 24 h. The solubilizing capacity of each system is based on visual observation at room temperature, 0°C (1 week), and 0°C (1 week) after crystallization. Crystallization is equivalent to adding the smallest possible number of crystals of each active ingredient to the solution. Crystallization is performed to avoid supersaturation of the active ingredients. The addition of crystals restores the thermodynamic stability of the sample. At a given concentration, if the mixture is clear (homogeneous liquid phase), the active ingredient is considered soluble in the solvent at that concentration. However, if turbidity, crystals, suspended particles, or sediment are present, the active ingredient is no longer soluble in the solvent, and maximum solubility has been reached. Maximum solubility is defined as the maximum amount of one or more active ingredients that can dissolve in the solvent system, equal to the amount at which the mixture remains clear.

[0225] The solvent in which we can achieve the highest concentration of active ingredient is the most efficient solvent for that active ingredient.

[0226] The solubility results of the solvent of the present invention, named GSA-18, obtained according to Example 3, at room temperature and 0°C, together with the corresponding solubility data of the solvent PolarClean as a reference, are shown in the table below.

[0227] As can be seen in these tables, the solvents of the present invention exhibit superior solubility performance compared to PolarClean for the following active ingredients: azoxystrobin, difenoconazole, and oxadiazon.

[0228] For other compounds, the solvents of this invention exhibit similar or slightly lower performance, but have the advantage of potential biological origin.

[0229]

[0230] 5. Solubility of different polymers

[0231] GSA-18 was tested as an alternative to NMP as a solvent for dissolving polymers. The results are presented in the table below. As can be seen, GSA-18 is a suitable alternative to the solvent NMP and can be used to manufacture battery electrodes for solid-state or Li-ion batteries, or for coatings, or for the production of antifouling membranes for a wide range of filtration applications. PVDF (Solef® brand) and Tecnoflon® are polymer binders that are typically dissolved in NMP (or DMF and DMAc) and then used to dispense a slurry (also known as a wet coating) of carbon materials and dissolved binders onto the substrate material: the electrode.

[0232] PVDF (Solef® 1015) is also used in the manufacture of microfiltration and ultrafiltration membranes for a wide range of filtration applications via the NIPS process (solvent-inducible phase separation). In NIPS, a polymer solution membrane is immersed in a solvent-free bath (water), inducing phase separation into a polymer-rich phase that forms the membrane matrix and a polymer-poor phase that forms the membrane pores. N-methyl-2-pyrrolidone (NMP) is used as the solvent medium because it can successfully dissolve PVDF.

[0233] Polyamide-imide (PAI) (Torlon® grade) is used as a high-performance coating material in both the automotive industry and high-end home appliances. A primary need here is to find good solvents to achieve coating formulations in liquid form. NMP, DMF, and DMAC are known as good solvents for this type of polymer.

[0234] .

Claims

1. A mixture comprising a compound having structure (IIIa) and a compound having structure (IIIb), a diamide compound optionally having formula (IIIc), and a diester compound optionally having formula (II): (IIIc): (II): 。 2. The mixture according to claim 1, comprising 75 to 95 wt% of esteramide (IIIa), 5 to 15 wt% of esteramide (IIIb), 0 to 8 wt% of diester precursor (II) and 0 to 8 wt% of diamide (IIIc).

3. A method for manufacturing the mixture according to claim 1 or 2, the method comprising an amidation step of dimethyl 2-methylsuccinate (DMMS, II).

4. The method according to claim 3, wherein the method uses dimethylamine (DMA) and is preferably catalyzed by sodium methoxide (MeONa).

5. The method according to claim 3 or 4, further comprising an additional step of synthesizing the DMMS(II) by hydrogenation of dimethyl itaconic acid (DMI, I), the additional step preferably using a Pd / C catalyst.

6. The method of claim 5, further comprising an additional step of synthesizing the DMI(I) by esterification of itaconic acid (IA) with methanol, the additional step preferably using methanesulfonic acid as a catalyst, and / or in the presence of a polymerization inhibitor, preferably hydroquinone.

7. Use of the mixture according to claim 1 or 2, or the mixture obtained by the method according to any one of claims 3 to 6, as a solvent.

8. The use according to claim 7, wherein the use is for agricultural formulations.

9. An agricultural formulation comprising an agriculturally active compound and a mixture according to claim 1 or 2, or a mixture obtained by any one of claims 3 to 6.

10. The use according to claim 9, wherein, This agricultural active compound is a fungicide, specifically selected from azoxystrobin, difenoconazole, and oxadiazon.

11. The use according to claim 8, wherein the use is for coating applications, membrane manufacturing, or solid-state batteries.

12. The use according to claim 8, wherein the use is for the recycling of polymers, particularly chemically resistant polymers such as PVDF or PVDC (polyvinylidene chloride).

13. The use according to claim 8, wherein the use is for preparing condensation polymers, particularly polyimides or polyesters or polyamides or polyamide-imides, particularly partially or fully aromatic condensation polymers such as aromatic polyamides (aromatic polyamides), in solution.

14. The use according to claim 8, wherein the use is as a cleaning solvent for cleaning equipment such as, for example, reactors, particularly polymerization reactors.

15. The use according to claim 8, wherein the use is as a solvent in household care formulations, for use in homes or public areas (hotels, offices, factories, etc.), for example, for formulating for cleaning hard surfaces such as floors, furniture surfaces and surfaces of kitchen and bathroom accessories, or tableware, or for use in industrial fields, for example, for degreasing manufactured products and / or for cleaning them.

Images