Use of cyclic ether derivatives as solvents

Abstract

The present invention relates to the use of cyclic ether derivatives as polar aprotic solvents, for example for dissolving agricultural active agents in agricultural formulations.

Description

Technical Field

[0001] This invention relates to the use of cyclic ether derivatives as polar solvents, for example, for dissolving agricultural surfactants in agricultural formulations. Background Technology

[0002] 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.

[0003] 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.

[0004] 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."

[0005] These concentrated formulations of agricultural compounds are typically diluted before agricultural use. Dilution by farmers usually involves mixing the agricultural chemical formulation with water.

[0006] 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.

[0007] 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.

[0008] In the field of emulsifiable concentrate (EC) formulations, there is a need for polar 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.

[0009] A common polar aprotic solvent used is Rhodiasolv® PolarClean, which exhibits good solubility and good toxicity / ecotoxicity characteristics. However, the agricultural market is now seeking higher-performance solvents with clean toxicity / ecotoxicity characteristics. Currently, only a limited number of commercially available high-performance solvents with clean toxicity / ecotoxicity characteristics exist. Examples of such solvents are N-butylpyrrolidone (NBP) and N,N-dimethyllactic acid.

[0010] The three solvents mentioned above (Rhodiasolv® PolarClean, N-butylpyrrolidone (NBP), and N,N-dimethyllactic acid) are miscible with water. For use in EC formulations, they must be blended with non-aqueous solvents that are typically much less polar to prevent crystallization of the active ingredient upon dilution in water and to ultimately provide a stable emulsion. Unfortunately, these non-aqueous solvents are particularly inefficient at dissolving the active ingredient, resulting in a significant reduction in the solubility of the final solvent blend.

[0011] To improve the solubility of active ingredients in EC formulations, two methods can be followed.

[0012] First, there is a need to develop new polar (and water-miscible) solvents that demonstrate improved solubility for a wide range of agrochemical active compounds. However, as mentioned, this approach is limited by the fact that blending with an aqueous immiscible solvent is necessary, which results in a significant reduction in the solubility of the active ingredient in the final solvent blend (solubility leveling caused by the aqueous immiscible solvent).

[0013] Therefore, it is necessary to develop new solvents that are less immiscible or non-aqueous to water, but still retain a certain degree of polarity so as to limit the reduction in dissolution efficiency when mixed with polar water-miscible solvents.

[0014] Therefore, the object of the present invention is to provide a polar solvent that is miscible with water and exhibits improved solubility for a wide range of agrochemical active compounds.

[0015] Another object of the present invention is to provide a solvent that does not necessarily need to be miscible with water but retains a certain degree of polarity, and can be blended with polar, water-miscible solvents without impairing the solubility of the resulting solvent blend. Summary of the Invention

[0016] This invention achieves these objectives by using compounds having the following formula (I) as solvents in agricultural formulations.

[0017]

[0018] (I)

[0019] in:

[0020] - m and n are integers from 0 to 3.

[0021] X and Y are independently selected from -CH2- and -O-

[0022] - R1, R2, R3 and R4 are independently selected from H and alkyl groups.

[0023] It has been found that cyclic ether derivatives according to formula (I) can be used as polar solvents with favorable solubility properties. In particular, compounds having formula (I) have been found to exhibit good ability to dissolve significant amounts of agrochemical active compounds, such as fertilizers (stabilizers) and pesticides, as well as high compatibility with many agrochemical active compounds.

[0024] Advantageously, compounds having formula (I) are eco-friendly solvents with good safety and sustainability characteristics, having no or very low hazard classifications and no or very low ecotoxicity. Specifically, US2011 / 0233474 discloses the use of mixtures of solvents, particularly tetrahydrofurfuryl alcohol (THFA), for dissolving NBPT (N-(n-butyl)thiophosphoric triamine) (a well-known fertilizer stabilizer). However, THFA is classified as a reproductive toxicity category 1B solvent. On the other hand, compounds having formula (I) are inert and stable (especially in acidic media), making them inherently non-reproductive and not forming reproductively toxic compounds like THFA. Furthermore, the applicant has unexpectedly discovered that these compounds retain high solubility despite structural changes and the introduction of stable ether functional groups compared to THFA. Detailed Implementation

[0025] The following definitions are relevant to embodiments of the present invention.

[0026] 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”.

[0027] 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.

[0028] 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.

[0029] As used in this article, the term "room temperature" refers to a temperature between 20°C and 30°C, typically 25°C.

[0030] 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.

[0031] 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 (cyclohexylphosphoric acid triamine).

[0032] As used herein, the term "formulation" refers to a mixture comprising at least the compound of the present invention and another component / compound. This mixture may be homogeneous (i.e., a solution) or heterogeneous (i.e., a dispersion, emulsion, suspension, or emulsion).

[0033] The term "% w / v" refers to the weight of the corresponding ingredient based on the total volume of the preparation.

[0034] The following further defines embodiments and preferred embodiments according to the present invention. Preferred embodiments are preferred individually or in combination.

[0035] In one aspect, the present invention relates to the use of compounds having formula (I) as solvents (i.e., in agricultural formulations).

[0036]

[0037] (I)

[0038] in:

[0039] - m and n are integers from 0 to 3.

[0040] X and Y are independently selected from -CH2- and -O-

[0041] - R1, R2, R3 and R4 are independently selected from H and alkyl groups.

[0042] In a preferred embodiment, R1 to R4 are independently selected from H and C1-C4 alkyl or alkoxy groups.

[0043] In formula (I), the following embodiments (alone or in combination) are preferred:

[0044] -m or n is equal to 1, but preferably both are equal to 1;

[0045] -X or Y is -CH2-, but preferably both are -CH2-;

[0046] -R1, R2, R3 or R4 are H, but preferably R1 to R4 are H.

[0047] Therefore, in a particularly preferred embodiment of the present invention:

[0048] -m and n are both equal to 1;

[0049] Both -X and Y are -CH2-; and

[0050] -R1 to R4 are H.

[0051] That is, within the framework of this invention, good results were obtained using BTHFE (bis(tetrahydrofurfuryl) ether). This compound also has the advantage of having a 100% Renewable Carbon Index (RCI). The Renewable Carbon Index (or RCI) measures sustainability by dividing the amount of carbon derived from renewable sources by the total amount of carbon in the active ingredient. For example, high-RCI surfactants contain a high percentage of carbon atoms from natural sources.

[0052] The use of compounds of formula (I) as solvents in this invention also includes their use as co-solvents and / or as crystallization inhibitors. Use as a co-solvent means that the compound of formula (I) is used in combination with at least one additional solvent. This at least one additional solvent may be a solvent for compounds of formula (I) or a solvent for compounds that do not have formula (I). Compounds of formula (I) also act as crystallization inhibitors, for example in emulsifiable concentrates, where the agriculturally active compound is present in a highly concentrated form, and then the concentrate is diluted in water by farmers for application to the field.

[0053] Compounds having formula (I) advantageously exhibit not only good to excellent solubility properties, but also preferably very good safety and sustainability characteristics, wherein there is no hazard classification or a very low hazard classification and no or very low ecotoxicity. This is especially true for BTHFE. A quantitative structure-activity relationship (QSAR) model was used to estimate the preliminary toxicity profile of BTHFE for human health and the environment, and no toxicity was identified for either humans or the environment.

[0054] Therefore, compounds having formula (I), and especially BTHFE, can generally be used as alternatives to toxic solvents such as N-methyl-2-pyrrolidone (NMP) or to other polar and eco-friendly solvents such as NBP (N-butyl-2-pyrrolidone), Rhodiasolv® PolarClean, N,N-dimethyllactic acid and Rhodiasolv® ADMA 10.

[0055] The cyclic ether derivatives according to formula (I) can be obtained by any method / process known to those skilled in the art. For example, in the specific case of BTHFE, reference can be made to the following publications: US2017233361, US9862694, WO16025677, US2015353518, WO 20000170, ChemistryOpen, 2016, Vol. 5, p. 297, and ACS Catalysis, 2020, Vol. 10, p. 3404. The raw materials used to prepare BTHFE include furfural or its derivatives, such as tetrahydrofurfuryl alcohol and furfuryl alcohol. It is well known that furfural is directly derived from lignocellulosic biomass, such as corn cobs, rice husks, and sawdust. Therefore, furfural and its derivatives (including BTHFE) have 100% RCI.

[0056] In another aspect, the present invention relates to an agricultural formulation (or agricultural chemical formulation) comprising an agriculturally active compound and a compound having formula (I), wherein the agriculturally active compound as described above may be used.

[0057] The agricultural formulation of the present invention may comprise:

[0058] a) At least one agronomic active compound (especially only one agronomic active compound, or a combination of different agronomic active compounds);

[0059] b) Compounds having formula (I) used as solvents or co-solvents;

[0060] c) Optionally at least one emulsifier and / or a surfactant; and

[0061] d) Optional ground water.

[0062] 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.

[0063] Agricultural active compounds are typically products in pure or highly concentrated form.

[0064] 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.

[0065] 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.

[0066] Non-limiting examples of fungicides suitable for use in this invention include: azoles, such as prothioconazole, flutriafol, difenoconazole, propiconazole, cyproconazole, tebuconazole, and imazalil; 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.

[0067] 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.

[0068] Specifically, the agricultural active compound is effective at 20°C and atmospheric pressure (i.e., 1.013 x 10⁻⁶).5 It 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.

[0069] 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.

[0070] 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).

[0071] 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.

[0072] 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).

[0073] 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.

[0074] 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.

[0075] 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.

[0076] Typically, the compound having formula (I) 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.

[0077] Several agriculturally active compounds can be combined in the agricultural formulation of the present invention.

[0078] The agricultural formulations according to the present invention may contain at least one biostimulant.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] The agricultural formulations according to the present invention may contain at least one plant growth regulator.

[0083] 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, p-chlorophenoxyacetic acid, dicamba, 2,4-dichloropropionic acid (dichl) orprop), 2,4,5-tetrapropionic acid (fenoprop), indole-3-acetic acid (IAA), indole-3-acetyl-DL-aspartic acid, indole-3-acetyl-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, methyl indole-3-acetate, naphthylacetamide, naphthaleneacetic acid (NAA), phenylacetic acid, doxycycline, potassium naphthenate, sodium naphthenate, 4-hydroxyphenylethanol, 4-CPPU, 6-benzylaminopurine (BA), 6-(γ,γ-dimethylallylamino)purine (2iP), 2-iP- 2HC1, 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 (GAn), ethylene, and abscisic acid.

[0084] The agricultural formulations according to the present invention may optionally contain at least one emulsifier.

[0085] 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.

[0086] 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.

[0087] Typically, the agricultural chemical formulations according to the present invention further comprise at least one surfactant.

[0088] Advantageously, the surfactants that can be used in this invention are selected from anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, and mixtures thereof.

[0089] Preferably, the surfactant is selected from anionic surfactants, nonionic surfactants, and mixtures thereof.

[0090] More preferably, the surfactant is selected from anionic surfactants, polyalkoxylated nonionic surfactants, and mixtures thereof.

[0091] The emulsifiers and surfactants that can be used are different from one or more agricultural active compounds.

[0092] As examples of anionic surfactants, the following can be mentioned without any intended limitations:

[0093] - 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,

[0094] - 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.

[0095] - Phosphate esters, more particularly selected from those comprising at least one straight-chain or branched, saturated, unsaturated, or aromatic hydrocarbon group, the hydrocarbon group comprising 8 to 40, 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 C10 -C 22 Alcohols; phosphoric acid and non-alkoxylated C8-C 22 Preferably C 10 -C 22 alcohol,

[0096] - 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).

[0097] 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.

[0098] As examples of nonionic surfactants, the following can be mentioned without any intended limitations:

[0099] - 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.

[0100] - 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.

[0101] - 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.

[0102] - 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.

[0103] Useful emulsifiers, particularly the following products, are all sold by the applicant:

[0104] - Soprophor® TSP / 724: A surfactant based on ethoxylated tristyrylphenol.

[0105] - Soprophor® 796 / P: A surfactant based on ethoxylated tristyrylphenol.

[0106] Soprophor® CY 8: A surfactant based on ethoxylated tristyrylphenol.

[0107] - Soprophor® BSU: A surfactant based on ethoxylated tristyrylphenol.

[0108] - Soprophor® S / 25: A surfactant based on ethoxylated tristyrylphenol.

[0109] Soprophor® 3D33: A surfactant based on ethoxylated tristyrylphenol phosphate.

[0110] - Alkamuls® RC: A surfactant based on ethoxylated castor oil.

[0111] - Alkamuls® OR / 36: A surfactant based on ethoxylated castor oil.

[0112] - Alkamuls® VO2003: A surfactant based on ethoxylated castor oil.

[0113] - Alkamuls® OL40: A surfactant based on ethoxylated dehydrated sorbitan hexaoleate.

[0114] - Alkamuls® T / 20: A surfactant based on ethoxylated dehydrated sorbitol esters.

[0115] - Geronol® TBE724: A surfactant based on ethoxylated tristyrylphenol.

[0116] - Geronol® TEB25: A mixture of surfactants based on ethoxylated castor oil, calcium dodecylbenzenesulfonate, and alkoxylated polymers.

[0117] - Rhodacal® 60 / B: A surfactant based on dodecylbenzene sulfonate.

[0118] - Rhodacal® 60 / BE: A surfactant based on dodecylbenzene sulfonate.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] The agricultural formulations according to the invention may further comprise at least one cosolvent different from the compound having formula (I).

[0123] The other solvent or co-solvent can typically be selected from:

[0124] - 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.

[0125] - 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.

[0126] More specifically, this cosolvent is selected from:

[0127] - 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;

[0128] - 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; 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.

[0129] - Mono-, di-, or tri-alkyl phosphates, such as triethyl phosphate; tributyl phosphate; or tri-2-ethylhexyl phosphate;

[0130] - Aliphatic, alicyclic, or aromatic ketones, such as dialkyl ketones; benzyl ketones; fenestrate ketones; acetophenones; cyclohexanones; alkylcyclohexanones; isophorones; cyclopentanones.

[0131] - Aliphatic, alicyclic, or aromatic alcohols, such as diols; 2-ethylhexanol; cyclohexanol; benzyl alcohol; tetrahydrofurfuryl alcohol;

[0132] - 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;

[0133] - Fatty acids, such as linoleic acid, linolenic acid, and oleic acid;

[0134] - Carbonates, such as propylene carbonate or butylene carbonate;

[0135] - Amides, such as alkyl dimethylamide, dimethyl-decanoamide; N-alkyl-pyrrolidone; dimethyl lactamide.

[0136] - Alkyl urea;

[0137] - Amines, such as alkanolamines and morpholines;

[0138] - Tetramethyl sulfone; sulfolane;

[0139] - Dimethyl sulfoxide;

[0140] - Halogenated alkanes or halogenated aromatic solvents, such as chloroalkanes or chlorobenzenes.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] Advantageously, the agricultural formulation according to the invention is effective at 20°C and atmospheric pressure (i.e., 1.013 x 10⁻⁶). 5 It is in liquid form at Pa, and can be in the form of a concentrate, diluted concentrate, or sprayable diluted concentrate of one or more agricultural active compounds.

[0145] 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).

[0146] 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).

[0147] 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).

[0148] 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.

[0149] In a specific embodiment, the agricultural formulation according to the present invention is in the form of an emulsifiable concentrate (EC).

[0150] 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).

[0151] According to one embodiment of the present invention, the agricultural chemical formulation according to the present invention is water-based.

[0152] 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.

[0153] According to this embodiment, the pH range is preferably from 1 to 11, and particularly from 2.5 to 9.5.

[0154] 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.

[0155] According to specific embodiments of the invention, agricultural formulations may advantageously comprise:

[0156] 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.

[0157] b) 5% to 90% by weight, preferably 10% to 90% by weight, particularly 30% to 90% by weight, for example 30% to 80% by weight, of the compound of the invention or a mixture of compounds of the invention according to the invention, relative to the total weight of the agricultural preparation.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] Conventional methods known for preparing agricultural formulations can be implemented. This can be achieved by simply mixing the components.

[0162] 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.

[0163] 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. Example

[0164] In the following examples, mixtures were prepared by dissolving an active ingredient (fungicide or fertilizer stabilizer) at a given concentration (g / L) in an indicated solvent. The mixtures were stirred at 60 rpm using a rotary drive over 24 hours at room temperature. The solubility of each system was based on visual observation at room temperature. At a given concentration, if the mixture was clear (homogeneous liquid phase), the active ingredient was considered soluble in the given solvent at that concentration. However, if a turbid solution, crystals, or sediment did occur, the active ingredient was considered insoluble in the given solvent, and the maximum solubility was determined, defined as the maximum amount of one or more active ingredients that could dissolve in the solvent system, equal to the amount at which the mixture remained clear.

[0165] Examples 1 and 2: Maximum solubility of different fungicides

[0166] Example 1

[0167] Based on the protocol described above, the maximum solubility of different fungicides was measured in both Rhodiasolv® Polarclean (with a renewable carbon index (RCI) of 0%) and BTHFE (RCI 100%). The maximum solubility (w / v) values ​​(in g / L solvent) at room temperature are summarized in Table 1 below:

[0168] Table 1

[0169]

[0170] These data indicate that BTHFE achieved acceptable (for tebuconazole), similar (for prothioconazole, pyraclostrobin, prochloraz and azoxystrobin) or even improved (for difenoconazole and azoxystrobin) performance in terms of solubility, while significantly improving RCI (from 0% (Polarclean) to 100% (BTHFE)).

[0171] Example 2

[0172] Based on the protocol described above, the maximum solubility of different fungicides was measured in Rhodiasolv® ADMA10 (with a Renewable Carbon Index (RCI) of 83%) and BTHFE (RCI 100%). The maximum solubility (w / v) values ​​(in g / L solvent) at room temperature are summarized in Table 2 below:

[0173] Table 2

[0174]

[0175] These data indicate that BTHFE achieved similar (for tebuconazole) or even improved (for prothioconazole, azoxystrobin, oxadiazon, prochloraz, difenoconazole and pyraclostrobin) performance in terms of solubility, while significantly increasing RCI (from 83% (Rhodiasolv® ADMA10) to 100% (BTHFE)).

[0176] Example 3: Maximum solubility of NBPT

[0177] Based on the protocol described above, the maximum solubility of NBPT (N-n-butyl)thiophosphoric triamine was measured in Rhodiasolv® Polarclean (with a renewable carbon index (RCI) of 0%), Rhodiasolv® ADMA10 (RCI 83%), and BTHFE (RCI 100%). The maximum solubility (w / v) values ​​(in g / L solvent) at room temperature are summarized in Table 3 below.

[0178] Table 3

[0179]

[0180] These data demonstrate that BTHFE achieves improved performance in dissolving NBPT compared to Rhodiasolv® Polarclean and ADMA10, while also significantly improving RCI.

Claims

1. Use of compounds having formula (I) as solvents in agricultural formulations. (I) in: - m and n are integers from 0 to 3. X and Y are independently selected from -CH2- and -O- - R1, R2, R3 and R4 are independently selected from H and alkyl groups.

2. The use according to claim 1, wherein, In the compound having formula (I): -m or n equals 1, but preferably both equal to 1; and / or -X or Y is -CH2-, but preferably both are -CH2-; and / or -R1, R2, R3 or R4 are H, but preferably R1 to R4 are H.

3. The use according to claim 1 or 2, wherein, The compound having formula (I) is BTHFE (bis(tetrahydrofurfuryl) ether).

4. The use according to any one of claims 1 to 3, wherein the use is for dissolving agricultural active compounds.

5. The use according to claim 4, wherein, The agricultural active compound is 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.

6. The use according to claim 4 or 5, wherein, The agricultural active compound is a pest control agent selected from the group consisting of herbicides, insecticides, acaricides, fungicides, algaecides, molluscicides, miticides, nematicides, biocides, and rodenticides, and mixtures thereof.

7. The use according to any one of claims 4 to 6, wherein, The agricultural active compound is selected from the following fungicides: azoles, such as prothioconazole, flutriafol, difenoconazole, propiconazole, cyproconazole, tebuconazole and imazalil; amphotericin B, such as azoxystrobin, oxadiazon, pyraclostrobin, fluazinam, pyraclostrobin; and carboxamides, such as chlorofluorobifenpyroxen, fluopyram, benzovindiflupyr and fluopyram; and mixtures thereof.

8. The use according to claim 4 or 5, wherein, The agricultural active compound is a fertilizer stabilizer selected from the group consisting of N-(n-butyl)thiophosphoric triamine (NBPT) and dicyandiamide (DCD), and mixtures thereof.

9. The use according to any one of claims 1 to 8, wherein the use is in an agricultural preparation.

10. The use according to claim 9, wherein, This agricultural formulation is a formulation or fertilizer formulation containing a pesticide, preferably an efficiency-enhancing fertilizer formulation.

11. The use according to claim 9 or 10, wherein, The agricultural formulation is in the form of an emulsifiable concentrate (EC), an emulsion concentrate in water (EW), a microemulsion (ME), a suspension (SE), an oil dispersion (OD), a dispersible concentrate (DC), a suspension concentrate (SC), a capsule suspension (CS), a soluble liquid (SL), or a flowable concentrate (FS) for seed treatment. It is preferably in the form of an emulsifiable concentrate (EC), an emulsion concentrate in water (EW), a microemulsion (ME), a suspension (SE), an oil dispersion (OD), a dispersible concentrate (DC), a capsule suspension (CS), or a soluble liquid (SL). More preferably, it is in the form of an emulsifiable concentrate (EC), an emulsion concentrate in water, a microemulsion concentrate, a suspension concentrate, an oil dispersion concentrate, or a dispersible concentrate. It is particularly preferably in the form of an emulsifiable concentrate.

12. An agricultural preparation comprising... a) an agricultural active compound as defined in any one of claims 5 to 8, and b) The compound as defined in any one of claims 1 to 3; d) Optionally, at least one co-solvent, c) Optionally, at least one emulsifier and / or one surfactant, and d) Optional ground water.

13. The agricultural formulation according to claim 12, wherein it is in the form defined in claim 11.

14. The agricultural formulation according to claim 12, comprising... a) at least one agricultural active compound as defined in any one of claims 5 to 7, preferably at least one pest control agent as defined in claim 6, in 0.01% to 90% by weight, preferably 5% to 60% by weight, relative to the total weight of the agricultural formulation; b) 5% to 90% by weight, preferably 10% to 90% by weight, particularly 30% to 90% by weight, for example 30% to 80% by weight, relative to the total weight of the agricultural formulation; c) at least one co-solvent, comprising 0.1% to 40% by weight, preferably 1% to 30% by weight, relative to the total weight of the agricultural formulation. 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, particularly 1% to 25% by weight, for example 1% to 5% by weight, relative to the total weight of the agricultural formulation, and 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.

15. The use according to any one of claims 1 to 14, wherein, The use of the compound having formula (I) as a solvent includes, preferably, its use as a cosolvent and / or crystallization inhibitor in agricultural formulations as defined in claims 12 to 14.

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