Bio-based beta-ether propionamide compounds as solvents

Abstract

The present invention relates to beta-ether propionamide compounds of formula (I) suitable as eco-friendly solvents.

Description

[0001] BIO-BASED BETA-ETHER PROPIONAMIDE COMPOUNDS AS SOLVENTS

[0002] TECHNICAL FIELD

[0003] The present invention relates to beta-ether propionamide compounds, suitable as eco-friendly solvents, e.g. in agriculture formulations.

[0004] TECHNICAL BACKGROUND

[0005] Industry uses many chemical compounds as solvents, for example for preparing chemicals and materials, for formulating chemical compounds, or for treating surfaces. Solvents are also used for the formulation of agricultural compounds, in particular phytosanitary active agents (fertilizers, pesticides...), for example in the form of emulsifiable concentrates (ECs) intended to be diluted in water by the farmer before being applied to a field.

[0006] In the case of fertilizers as active agents, nitrogen fertilizer stabilizers, such as urease or nitrification inhibitors, are generally applied together with the fertilizer as enhanced efficiency fertilizer (EEF) into or onto the soil. This ensures that the stabilizer comes into contact, together with the fertilizer, with the soil. The nitrogen fertilizer stabilizers are dissolved in a polar solvent and can be incorporated in the fertilizer by adding this solution into the melt prior to granulation or prilling of the fertilizer. A process of this kind is described for urease inhibitors in U.S. Patent No. 5,352,265, for example.

[0007] The industry in the field of agriculture attempts to achieve a concentration of the agricultural active compound(s) as high as possible in the respective formulation since a high concentration of the agricultural compound(s) allows the volumes to be applied to be reduced and, as a consequence, entails savings with regard to the adjuvant materials applied and with regard to packaging and logistics. Highly-concentrated stable formulations and coformulations with environmentally friendly adjuvants are therefore of interest as a matter of principle.

[0008] For agricultural active compounds with a low or relatively low water solubility, the use of appropriate solvents is especially interesting to prepare concentrated liquid formulations, in the form of emulsifiable concentrates (EC), concentrated emulsions in water (EW), microemulsions (ME), suspoemulsions (SE), oil dispersions (OD), dispersible concentrates (DC). More details on the definitions of above-mentioned formulations can be found in the “Guidance document for the generation of data on the physical, chemical and technical properties of plant protection products under regulation (EC) N° 1107 / 2009 of the EU parliament and council on placing plant protection products on the market”.

[0009] Such concentrated formulations of agricultural compounds are generally diluted prior to agricultural use. The dilution effected by the farmer is generally performed by mixing the agrochemical formulation with water.

[0010] In addition, certain solid agricultural active compounds are often difficult to formulate. For certain agricultural compounds, it is difficult to produce concentrated formulations that are easy for the farmer to dilute, stable and free of substantial drawbacks (real or perceived) with regard to safety, toxicity and / or ecotoxicity. For certain agricultural compounds, it is difficult to formulate at relatively high concentrations with sufficient stability. In particular, it is necessary to avoid the appearance of crystals, in particular at low temperature and / or during dilution and / or during storage of the composition, in particular at low temperature. The crystals may have harmful effects, especially blocking the filters of the devices used for spreading the dilute composition, blocking the spraying devices, reducing the overall activity of the formulation, creating unnecessary problems of waste-management procedures for removing the crystals, and / or causing poor distribution of the agricultural material(s) on the agricultural field.

[0011] The agrochemical industry is therefore constantly looking for new solvents and solvent compositions having properties that are satisfactory for agricultural application, like for example, good solubilization efficiency for a wide range of agricultural compounds. In addition, the cost of the solvent compositions should generally be modest, and preferably they should have a favourable toxicology and / or ecotoxicology profile, in particular low toxicity and / or low hazard potential, and / or low volatility (low VOC - volatile organic compounds) and / or advantageously high degree of biodegradability and / or renewability.

[0012] There are a limited number of eco-friendly polar solvents on the market, including NBP (N-butyl-2-pyrrolidone), Cyrene® (Dihydrolevoglucosenone), N,N-dimethyl lactamide, Rhodiasolv® PolarClean, and Rhodiasolv® ADMA 10.

[0013] However, these solvents are not always suitable for all purposes, including the dissolution of agricultural active compounds such as pesticides and fertilizers at high concentration, while generally also ensuring an acceptable viscosity of the solution and a storage stability over a range of different temperatures including low temperatures, such as e.g. 0°C or lower.

[0014] Moreover, if the use of specific solvent systems based on a single solvent such as N-methyl-2-pyrrolidone (NMP) can enable the dissolution of a certain number of agricultural materials, it is however known as presenting reprotoxicity hazards, especially for the operatives and users handling it.

[0015] Therefore, it is an object of the present invention to provide a preferably bio-based and eco-friendly polar aprotic solvent that has good to excellent solubilization properties for the dissolution of agricultural active compounds (e.g. pesticides and fertilizer stabilizers) at high concentrations, while generally also ensuring storage stability over a range of different temperatures including low temperatures, such as e.g. 0°C or lower.

[0016] SUMMARY OF THE INVENTION

[0017] These objects have surprisingly been solved by a compound of formula (I) wherein

[0018] R1and R2are independently selected from -(Ci-Ce)alkyl including - (Ci)alkyl, -(C2)alkyl, -(Cs)alkyl, -(C4)alkyl, -(Cs)alkyl, and -(Ce)alkyl, or R1and R2form with the nitrogen atom a heterocycle containing 4 to 8 carbon atoms;

[0019] R3is a residue of formula (Ila) or formula (lib) wherein

[0020] X is -CH2- or -O-; and

[0021] R4is hydrogen or -(Ci-C4)alkyl including -(Ci)alkyl, -(C2)alkyl, - (Cs)alkyl, -(C4)alkyl.

[0022] It has been found that the compounds of formula (I) are advantageously eco-friendly solvents, which have good safety and sustainable profile, with none or very low hazard classification and none or very low ecotoxicity, and are furthermore excellent solvents. In particular, it has been found that the compounds of the present invention are good, preferably excellent solvents for dissolving pesticides, for example fungicides, herbicides, insecticides, and / or (nitrogen) fertilizer stabilizers such as urease and nitrification inhibitors.

[0023] The present invention further relates a method for the production of the compounds of the present invention, comprising the step of reacting an alcohol R3-H and a compound of the following formula (III) wherein R1, R2and R3are defined as above, in the presence of a catalytic amount of a base. In a further aspect, the present invention relates to a composition or formulation comprising a compound of the present invention, or a mixture of compounds of the present invention.

[0024] In a further aspect, the present invention relates to the use of the compounds of the present invention as solvents, in particular in agriculture formulations for plant protection products, such as e.g. pesticides, for biostimulants, biologicals, plant growth regulator, and in enhanced efficiency fertilizer formulations containing an urease or nitrification inhibitor.

[0025] DETAILED DESCRIPTION OF THE INVENTION

[0026] The following definitions are relevant in connection with the embodiments of the present invention.

[0027] The meaning of the term “comprising” is to be interpreted as encompassing all the specifically mentioned features as well optional, additional, unspecified ones, whereas the term “consisting of’ only includes those features as specified. Therefore, “comprising” includes as a limiting case the composition specified by “consisting of’.

[0028] The term “wt. %” refers to the amount of the respective ingredient by weight based on the total amount by weight of the composition, unless noted otherwise.

[0029] The term “% w / v“ refers to the weight amount of the respective ingredient based on a total volume of the composition.

[0030] As used herein, the singular forms "a", "an", and "the" include both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a pesticide" means one pesticide or more than one pesticide.

[0031] The term “(Cx-Cy)alkyl” as used herein denotes in each case a straightchain or branched alkyl group having from x to y carbon atoms. Examples of a (Ci-Ce)alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3 -methylbutyl, 2,2- dimethylpropyl, 1 -ethylpropyl, 1,1 -dimethylpropyl, 1,2-dimethylpropyl, n- hexyl, 1 -methylpentyl, 2-methylpentyl, 3 -methylpentyl, 4-methylpentyl, 1,1- dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3, 3 -dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2- trimethylpropyl, 1,2,2-trimethylpropyl, 1 -ethyl- 1 -methylpropyl, and l-ethyl-2- m ethylpropyl. Non-limiting examples of the term “heterocycle containing from 4 to 8 carbon atoms” comprises pyrrolidine, piperidine, piperazine, and morpholine.

[0032] Non-limiting examples of the term “pesticide” comprises insecticides, fungicides, herbicides, acaricides, algicides, molluscicides, rodenticides, nematicides, biocides and miticides. Specific examples of pesticides can be found in the book “Sittig’s handbook of Pesticides and Agricultural Chemicals”, 2ndedition, William Andrew Publishing, 2015.

[0033] The term “nitrogen fertilizer stabilizer” as used herein refers to an agent that prevents or slow down kinetics of biodegradation of the fertilizer. Nonlimiting examples are urease or nitrification inhibitors, such as NBPT (N-(n- butyl)thiophosphoric triamide), DCD (dicyandiamide) and NPPT (N-(n- propyl)thiophosphoric triamide). Nitrification inhibitors delay the bacterial oxidation of the ammonium ion in fertilizers by inhibiting the activity of Nitrosomonas bacteria in the soil, which transform ammonium into nitrite. Urease inhibitors inhibit the transformation of urea to ammonia and CO2. Fertilizer containing fertilizer stabilizer is often referred to as slow- or controlled-release fertilizer or enhanced efficiency fertilizer (EEF). Non-limiting examples of nitrification inhibitors comprise DCD, DMPP (3,4-dimethylpyrazole phosphate), nitrapyrin (2-chloro-6-(trichloromethyl)pyridine, TU (thiourea), MT (l-mercapto-l,2,4-triazole), AM (2-amino-4-chloro-6-methyl pyrimidine, ASU (l-amide-2-thiourea), HPLC (lH-l,2,4-triazole), 3,4-dimethylpyrazole succinic (DMPSA). Non-limiting examples of urease inhibitors comprise NBPT, NPPT and CNPT (cylohexylphosphoric triamide).

[0034] The term “composition” as used herein refers to a mixture comprising at least the compound of the invention and another ingredient / compound. This mixture may be homogeneous (i.e. a solution) or heterogeneous (i.e. a dispersion, emulsion, suspension, suspoemulsion).

[0035] The term "room temperature" as used herein refers to a temperature of 20 to 30°C, typically to a temperature of 25°C.

[0036] The embodiments and preferred embodiments according to the invention are further defined hereinafter. The preferred embodiments are preferred alone or in combination. Further, it is to be understood that the following preferred embodiments refer to all aspects of the present invention, i.e. the compound, the method, the composition as well as the use of the compound. In an embodiment, the present invention relates to a compound of formula (I): wherein

[0037] R1and R2are independently selected from -(Ci-Ce)alkyl including - (Ci)alkyl, -(C2)alkyl, -(Cs)alkyl, -(C4)alkyl, -(Cs)alkyl, and -(Ce)alkyl, or R1and R2form with the nitrogen atom a heterocycle containing 4 to 8 carbon atoms;

[0038] R3is a residue of formula (Ila) or formula (Uh) wherein

[0039] X is -CH2- or -O-; and

[0040] R4is hydrogen or -(Ci-C4)alkyl including -(Ci)alkyl, -(C2)alkyl, - (Cs)alkyl, -(C4)alkyl. In a preferred embodiment, R1and R2are independently selected from - (Ci-C3)alkyl including -(Ci)alkyl, -(C2)alkyl, -(C3)alkyl. In a more preferred embodiment, R1and R2is methyl.

[0041] In a further preferred embodiment, R4is hydrogen or methyl. In a further preferred embodiment, R3is a residue of formula (Ila), X = -CH2- and R4= H; or R3is a residue of formula (Ila), X = -O- and R4= methyl; or R3is a residue of formula (Ila), X = -O- and R4= H; or R3is a residue of formula (lib), X = -O- and R4= H; or R3is a residue of formula (lib), X = -O- and R4= methyl.

[0042] Particularly preferred are compounds, wherein R1= R2= methyl, R3is a residue of formula (Ila), X = -CH2- and R4= H (corresponding to compound la prepared in Example 1); or R1= R2= methyl, R3is a residue of formula (Ila), X = -O- and R4= methyl (corresponding to compound lb prepared in Example 2); or R1= R2= methyl, R3is a residue of formula (Ila), X = -O- and R4= H (corresponding to compound Ic prepared in Example 3); or R1= R2= methyl, R3is a residue of formula (lib), X = -O- and R4= H (corresponding to compound Id prepared in Example 3); or R1= R2= methyl, R3is a residue of formula (lib), X = -O- and R4= methyl.

[0043] Especially preferred in the present invention is compound la (e.g. prepared in Example 1).

[0044] The compounds of the present invention can also be used as a mixture. Advantageously, the compounds of formula (I) have good to excellent solubilization properties and have preferably very good safety and sustainable profiles, with none or very low hazard classification and none or very low ecotoxicity.

[0045] Preferably, the compounds of formula (I) have a renewable carbon index (RCI) of at least 0.2, in particular ranging from 0.2 to 1, for instance 0.25 to 1, including renewable carbon indices (RCI) in the range of 0.3 to 1, 0.4 to 1, 0.5 to 1, 0.6 to 1 and 0.8 to 1.

[0046] Renewable carbon commonly entails all carbon sources that avoid or substitute the use of any additional fossil carbon from the geosphere. Renewable carbon can come from the biosphere, atmosphere or technosphere, but not from the geosphere.

[0047] Renewable carbon is here defined as carbon derived from recently living plant or animal organisms (as opposed to carbon derived from fossil carbon which is coal, oil or petroleum based), as well as carbon derived from CO2 capture.

[0048] Renewable Carbon Index (RCI) is defined as the value calculated by dividing the number of renewable carbons by the total number of carbons in the entire molecule. For example, if 80% of the number of carbons present is renewable carbon then the RCI is 0.8.

[0049] In an embodiment, the present invention relates to a method for the production of the compounds of the present invention, comprising the step of reacting an alcohol R3-H and a compound of the following formula (III) wherein R1, R2and R3are defined as above, in the presence of a catalytic amount of a base.

[0050] The method of the present invention involves C-O-bond formation between the alcohol R3-H and the compound of formula (III) by conjugated addition, which allows straight-forward and cost-efficient access of the compounds of the present invention.

[0051] The base is used in catalytic amounts, which means that it is used in sub-stoichiometric amounts in relation to the alcohol R3-H and the compound of the following formula (III). Suitable bases include alkoxide bases, such as e.g. sodium methylate (NaOMe).

[0052] Typically, the base is added to a mixture of the alcohol R3-H and the compound of formula (III). Preferably, the reaction between the alcohol R3-H and the compound of formula (III) is carried out neat, i.e. without the need of using an additional solvent. This further adds to the eco-friendliness and cost-efficacy of the method of the present invention.

[0053] Preferably, the reaction is carried out at room temperature.

[0054] The reaction progress can be monitored by routine techniques known to the skilled person, such as e.g. 'H NMR.

[0055] It is known by the person skilled in the art that those conjugate addition reactions are equilibrated reactions and it has surprisingly been found that under the conditions described in the present case, a very high conversion level for the reactants (the alcohol R3-H and / or the compound of formula (III)) can be attained. The conversion level for the alcohol R3-H and / or the compound of formula (III) is at least 50%, preferably at least 60% and even more preferably at least 70%. This high conversion level is a technical and economical advantage as only a minimum amount of unreacted reagents needs to be recycled.

[0056] Preferably, the base catalyst is neutralized after the maximum level of conversion has been reached. The neutralization step is typically carried out by adding an acid to the reaction mixture, such as e.g. H3PO4, until a pH between 5.5 and 8.0 has been reached, when measured in aqueous solution after 10% dilution.

[0057] The unconverted reactants are preferably removed by distillation in vacuum and can be recycled for the next batch.

[0058] Precipitated salt species coming from base catalyst neutralization can be removed by simple filtration or can be separated from the product (I) through vacuum distillation of the product, the salts remaining in the boiler. Solvents involved in this step can be removed by distillation in vacuum.

[0059] The resulting crude product may optionally be further purified by methods known in the art, such as (vacuum) distillation, filtration, liquid-liquid extraction, crystallization (for solid impurities), or column chromatography.

[0060] In an embodiment, the present invention relates to a composition comprising the compound of the present invention or a mixture of compounds of the present invention. This composition may be part of a formulation aimed at a specific function, preferably an agriculture formulation or an enhanced efficiency fertilizer formulation comprising the active ingredient(s) or / and the fertilizer compound(s) advantageously at a high concentration in view of the good to excellent solubilization properties of the compounds of the present invention.

[0061] The compound of the present invention and the mixture of compounds of the present invention have advantageously a great solubilization efficiency. In particular, they present a good ability for solubilization of significant quantities of agricultural active compounds (e.g. pesticides), and a high compatibility with many agricultural active compounds combined together, in order for example to enable an enhanced biological efficacy.

[0062] Since the compounds of the invention are also advantageously eco- friendly solvents and have preferably very good safety and sustainable profile, the composition of the present invention may also be part of a cleaning formulation, a stripping formulation, a degreasing formulation, a lubricant or textile formulation, a coating formulation, for example a paint formulation or a pigment or ink formulation.

[0063] In an embodiment, the compound or composition of the present invention forms part of an agriculture formulation, preferably a concentrated agriculture formulation, i.e. a formulation comprising an agricultural active compound.

[0064] The agriculture formulation of the present invention may comprise: a) at least one agricultural active compound (in particular only one agricultural active compound, or a combination of different agricultural active compounds); b) the compound of the invention or a mixture of compounds of the invention, generally as solvent; c) optionally at least one emulsifier or / and one surfactant; and d) optionally water.

[0065] In the agriculture formulation according to the invention, the compound(s) of the invention is (are) preferably chosen among the compounds wherein R1= R2= methyl, R3is a residue of formula (Ila), X = -CH2- and R4= H; or R1= R2= methyl, R3is a residue of formula (Ila), X = -O- and R4= methyl; or R1= R2= methyl, R3is a residue of formula (Ila), X = -O- and R4= H; or R1= R2= methyl, R3is a residue of formula (lib), X = -O- and R4= H; or R1= R2= methyl, R3is a residue of formula (lib), X = -O- and R4= methyl. More advantageously, the compound of the invention comprised in the agriculture formulation according to the invention is a compound wherein R1= R2= methyl, R3is a residue of formula (Ila), X = -CH2- and R4= H.

[0066] As used herein, the term “agricultural active compound” means an active ingredient used in particular to the practice of farming, including cultivation of the soil for the growing of crops. However, the use of agricultural active compound is not limited to application to crops. Agricultural active compounds (or materials) may be applied to any surface, e.g., for the purpose of cleaning or aiding or inhibiting growth of a living organism. Other non-crop applications include, but are not limited to, application to turf and ornamentals, and application to railroad weed.

[0067] The agricultural active compounds are generally products in pure or highly concentrated form.

[0068] The agricultural active compounds are preferably chosen from pesticides (including biopesticides), fertilizers, fertilizer stabilizers, nutrients, biostimulants, plant growth regulators, natural plant defense enhancers, inoculants and mixtures thereof.

[0069] Advantageously, the agriculture formulation according to the invention comprises at least one pesticide.

[0070] For example, the at least one pesticide may be chosen from fungicides, herbicides, insecticides, acaricides, algicides, molluscicides, miticides, nematicides, biocides and rodenticides.

[0071] Non-limiting examples of fungicides suitable for use in the agriculture formulation of the present invention include azoles such as e.g. prothioconazole, epoxiconazole, difenoconazole, propi conazole, cyproconazole, tebuconazole; strobilurins such as e.g. azoxystrobin, trifloxystrobin, picoxystrobin, fluoxastrobin, pyraclostrobin; and SDHIs (carboxamides) such as bixafen, fluxapyroxad, benzovindiflupyr, fluopyram; and mixtures thereof.

[0072] The agricultural active compounds can be water-insoluble, at 20°C and at atmospheric pressure (i.e., 1.013xl05Pa).

[0073] In particular, the agricultural active compounds can be soluble in water to no more than 100 g / L, generally no more than 20 g / L, notably no more than 5 g / L, for instance no more than 1 g / L and even no more than 0.2 g / L, at 20°C and at atmospheric pressure (i.e., 1.013xl05Pa).

[0074] In a further embodiment, the compound or composition of the present invention forms part of a fertilizer formulation, preferably an enhanced efficiency fertilizer formulation, which comprises a fertilizer and / or a fertilizer stabilizer, in particular a nitrogen fertilizer and / or a nitrogen fertilizer stabilizer and / or a urease and / or nitrification inhibitor.

[0075] The fertilizer and / or a fertilizer stabilizer, in particular the nitrogen fertilizer and / or nitrogen fertilizer stabilizer and / or urease and / or nitrification inhibitor may be / ' / -(n-butyl)thiophosphoric acid triamide (NBPT) and / or dicyandiamide (DCD).

[0076] In another embodiment, said fertilizer formulation further comprises at least one biostimulant, one plant growth regulator, one natural plant defense enhancer and / or one inoculant.

[0077] In another embodiment, said fertilizer formulation further comprises at least one pesticide, for example an herbicide, an insecticide, a fungicide, an acaricide, an algicide, a molluscicide, a miticide, a nematicide, a biocide or a rodenticide, for instance a raticide.

[0078] Generally, the amount of agricultural active compound(s) in the agriculture formulation of the invention ranges from 0.01 to 90% by weight, preferentially from 0.1 to 90% by weight more preferentially from 0.1 to 80% by weight; even more preferentially from 0.5 to 70% by weight; better from 1 to 65% by weight, in particular from 5 to 60% by weight, and for instance from 10 to 60% by weight, relative to the total weight of the agriculture formulation. According to a particular embodiment of the invention (concentrated composition), the total content of agricultural active compound(s) in the agriculture formulation ranges from 5 to 90% by weight, preferentially from 5 to 70% by weight, more preferentially from 5 to 60% by weight, and in particular from 10 to 60% by weight, relative to the total weight of the agriculture formulation.

[0079] According to another particular embodiment of the invention (diluted composition), the total content of agricultural active compound(s) in the agriculture formulation ranges from 0.01 to 3% by weight, preferentially from 0.05 to 2% by weight, and more preferentially from 0.1 to 1% by weight, relative to the total weight of the agriculture formulation.

[0080] Generally, the compound of the invention or the mixture of compounds of the invention represents from 10 to 99.9% by weight, preferentially from 10 to 99% by weight, more preferentially from 20% to 95% by weight, in particular from 30% to 90% by weight, for instance from 30% to 80% by weight, relative to the total weight of the agrochemical formulation.

[0081] The present invention also relates to the use of the compounds of the present invention as a solvent, co-solvent and / or crystallization inhibitor, in particular in agriculture formulations comprising an active ingredient and fertilizer formulations comprising a fertilizer and / or a fertilizer stabilizer, in particular a nitrogen fertilizer and / or a nitrogen fertilizer stabilizer and / or a urease and / or nitrification inhibitor.

[0082] The compound of the present invention may also be used as a coalescing agent, for instance in aqueous paint formulations.

[0083] The use as a solvent (or co-solvent) in agriculture formulations is particularly advantageous.

[0084] The compound of the invention may be used in an agriculture formulation comprising an active ingredient, for instance a pesticide.

[0085] The compound of the present invention may also be used in a fertilizer formulation, preferably an enhanced efficiency fertilizer formulation, comprising a fertilizer and / or a fertilizer stabilizer, in particular a nitrogen fertilizer and / or a nitrogen fertilizer stabilizer and / or a urease and / or nitrification inhibitor.

[0086] The term “solvent” may especially denote a product that is liquid at the usage temperature, which may contribute to rendering a solid substance liquid, or to preventing / retarding the solidification or crystallisation of material in a liquid form. It may generally have a melting point less than or equal to 20°C, in particular 5°C, for example 0°C.

[0087] As previously mentioned, it is possible to combine several agricultural active compounds in the agriculture formulation of the invention comprising the compound of the invention or a mixture of compounds of the invention.

[0088] The compound of the present invention may also be used generally as a replacement for toxic solvents such as N-Methyl-2-Pyrrolidone (NMP) or as a replacement for other polar and eco-friendly solvents, such as NBP (N-butyl-2- pyrrolidone), Cyrene™ (Dihydrolevoglucosenone), Rhodiasolv® PolarClean, N,N-dimethyl lactamide and Rhodiasolv® ADMA 10.

[0089] The compound of the present invention may be preferably used for the solubilization of an active ingredient in an agriculture formulation.

[0090] The agriculture formulation according to the invention may optionally comprise at least one biostimulant.

[0091] The term “biostimulanf ’ is preferably intended to mean a compound which may enhance metabolic or physiological processes such as respiration, photosynthesis, nucleic acid uptake, ion uptake, nutrient delivery, or a combination thereof.

[0092] Generally, this is a substance or microorganism that, when applied to seeds, plants or on the rhizosphere, can stimulate natural processes to enhance or benefit nutrient uptake, nutrient use efficiency, tolerance to abiotic stress, or crop quality and yield. Non-limiting examples of biostimulants include seaweed extracts (e.g., ascophyllum nodosum), humic acids (e.g., potassium humate), fulvic acids, myoinositol, glycine, and combinations thereof.

[0093] The agricultural formulation according to the invention may optionally comprise at least one plant growth regulator.

[0094] Plant growth regulators mean active ingredients used to influence the growth characteristics of plants. Examples of plant growth regulators which may be used in the present invention include, but are not limited to: 1- naphthaleneacetic acid, 1 -naphthaleneacetic acid -salt, 1-napthol, 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, 2-naphthoxyacetic acid sodium salt, 3-chloro-4-hydroxyphenylacetic acid, 3-indoleacetic acid, 4- biphenylacetic acid, 4-chlorophenoxyacetic acid (4-CPA), 4- hydroxyphenylacetic acid, 6-benzylaminopurine, auxindole, a-naphthaleneacetic acid K-salt, B-naphfhoxyacetic acid, p-chlorophenoxyacetic acid, dicamba, dichlorprop, 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 (IB A), indole-3 - butyric acid K-salt, indole-3 -propionic acid; a-naphthaleneacetic acid, methyl indole- 3 -acetate, naphthaleneacetamide, naphthaleneacetic acid (NAA), phenylacetic acid, picloram, potassium naphthenate, sodium naphthenate, 4-hydroxyphenethyl alcohol, 4-CPPU, 6-benzylaminopurine (BA), 6-(Y,Y-dimethylallylamino)purine (2iP), 2-iP- 2HC1, adenine, adenine hemisulfate, benzyladenine, kinetin, meta- topolin, N6- benzoyladenine, N- benzyl-9-(2 -tetrahydropyranyl) adenine (BP A), N-(2-chloro-4- pyridyl)-N-phenylurea, gibberellic acid (GA3), gibberellins, gibberellins A4 + A7 (GA n), ethylene and abscisic acid.

[0095] The agriculture formulation (or agrochemical formulation) according to the invention may optionally comprise at least one emulsifier.

[0096] Emulsifiers are agents that are intended to facilitate emulsification after the formulation is placed in the presence of water, and / or stabilisation (over time and / or in temperature) of the emulsion, for example by avoiding separation of the phases.

[0097] Generally, the total amount of emulsifier(s) in the agriculture formulation according to the invention, ranges from 0.05 to 40% by weight, preferentially from 0.1 to 35% by weight, more preferentially from 0.5 to 30% by weight, in particular from 1 to 25% by weight, for instance from 1 to 5% by weight, relative to the total weight of the agriculture formulation.

[0098] Generally, the agrochemical formulation according to the invention further comprises at least one surfactant.

[0099] Advantageously, the surfactants that may be used in the invention are chosen from anionic, non-ionic, cationic, amphoteric or zwitterionic surfactants, and mixtures thereof.

[0100] Preferentially, the surfactants are chosen from anionic surfactants, nonionic surfactants, and mixtures thereof.

[0101] More preferentially, the surfactants are chosen from anionic surfactants, polyalkoxylated non-ionic surfactants, and mixtures thereof

[0102] The emulsifiers and surfactants that may be used are different from the agricultural active compound(s).

[0103] By way of examples of anionic surfactants, mention may be made without any intended limitation thereto, of:

[0104] - alkylsulfonic acids, arylsulfonic acids, optionally substituted with one or more hydrocarbon groups, and the acid function of which is partly or totally salified, like C8-C50 alkylsulfonic acids, more particularly C8-C30, preferably C10-C22 alkylsulfonic acids, benzenesulfonic acids, naphthalenesulfonic acids, substituted with one to three C1-C30, preferably C4-C16 alkyl and / or C2-C30, preferably C4-C16 alkenyl groups,

[0105] - mono- or di-esters of alkylsulfosuccinic acids, of which the linear or branched alkyl portion is optionally substituted with one or more linear or branched C2-C4 hydroxylated and / or alkoxylated (preferably ethoxylated, propyxylated, ethopropoxylated) groups, - phosphate esters more particularly selected from among those comprising at least one linear or branched, saturated, unsaturated or aromatic hydrocarbon group, comprising 8 to 40 carbon atoms, preferably 10 to 30, optionally substituted with at least one alkoxylated (ethoxylated, propoxylated, ethopropoxylated) group. In addition, they comprise at least one phosphate ester group, mono- or di-esterified such that it is possible to have one or two free or partly or totally salified groups. The preferred phosphate esters are of the type of the mono- and di-esters of phosphoric acid and of alkoxylated (ethoxylated and / or propoxylated) mono-, di- or tri-styrylphenol, or alkoxylated (ethoxylated and / or propoxylated) mono-, di- or trialkylphenol, optionally substituted with one to four alkyl groups; of phosphoric acid and of an alkoxylated (ethoxylated or ethopropoxylated) C8-C30, preferably C10-C22 alcohol; of phosphoric acid and of a non-alkoxylated C8-C22, preferably C10-C22 alcohol,

[0106] - sulfate esters obtained from saturated or aromatic alcohols optionally substituted with one or more alkoxylated (ethoxylated, propoxylated, ethopropoxylated) groups, and for which the sulfate functions appear in the free acid form, or are partly or totally neutralised. As an example, mention may be made of sulfate esters more particularly obtained from saturated or unsaturated C8-C20 alcohols, which may comprise 1 to 8 alkoxylated (ethoxylated, propoxylated, ethopropoxylated) units ; sulfate esters obtained from polyalkoxylated phenol, substituted with 1 to 3 saturated or unsaturated C2- C30 hydroxycarbon groups, and in which the number of alkoxylated units is comprised between 2 and 40 ; the sulfate esters obtained from polyalkoxylated mono-, di- or tri-styrylphenol in which the number of alkoxylated units varies from 2 to 40.

[0107] The anionic surfactants may be in the acid form (they are potentially anionic), or in a partly or totally salified form with one counter-ion. The counterion may be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or moreover even an ammonium ion of formula N(R)4 + in which the R groups, either identical or different, represent a hydrogen atom or a C1-C4 alkyl group optionally substituted with an oxygen atom. By way of examples of non-ionic surfactants, mention may be made without any intended limitation thereto, of:

[0108] - polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated) phenols substituted with at least one C4-C20, preferably C4-C12 alkyl group, or substituted with at least one alkylaryl group, the alkyl portion of which is a Cl- C6 alkyl. More particularly, the total number of alkloxylated units is comprised between 2 and 100. As an example, mention may be made of polyalkoxylated mono-, di- or tri-(phenylethyl) phenols, or polyalkoxylated nonylphenols. Amongst the ethoxylated and / or propoxylated, sulfated and / or phosphated di- or tri-styrylphenols, mention may be made of ethoxylated di-(phenyl-l- ethyl)phenol, containing 10 oxy ethylene units ; ethoxylated di-(phenyl-l- ethyl)phenol, containing 7 oxy ethylene units ; sulfated ethoxylated di-(phenyl-l- ethyl)phenol, containing 7 oxy ethylene units ; ethoxylated tri-(phenyl-l- ethyl)phenol, containing 8 oxy ethylene units ; ethoxylated tri-(phenyl-l- ethyl)phenol, containing 16 oxy ethylene units ; sulfated ethoxylated tri-(phenyl- l-ethyl)phenol, containing 16 oxy ethylene units ; ethoxylated tri-(phenyl-l- ethyl)phenol, containing 20 oxyethylene units ; phosphated ethoxylated tri- (phenyl-1 -ethyl) phenol, containing 16 oxy ethylene units.

[0109] - polyalkoxylated (ethoxylated, propyxylated, ethopropoxylated) C6- C22 fatty acids or alcohols. The number of alkoxylated units is comprised between 1 and 60. The term ethoxylated fatty acid includes both the products obtained by ethoxylation of a fatty acid by ethylene oxide as well as those obtained by esterification of a fatty acid by a polyethylene glycol.

[0110] - polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated) triglycerides of vegetable or animal origin. Thus, may be included triglycerides from lard, tallow, ground nut oil, butter oil, cotton seed oil, flax oil, olive oil, palm oil, grapeseed oil, fish oil, soya bean oil, castor oil, rapeseed oil, coprah oil, coconut oil, and comprising a total number of alkoxylated units comprised between 1 and 60. The term ethoxylated triglyceride makes reference both to products obtained by ethoxylation of a triglyceride with ethylene oxide as well as to those obtained by transesterification of a triglyceride with a polyethylene glycol. - sorbitan esters, optionally polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated), more particularly the cyclised sorbitol esters of C10-

[0111] C20 fatty acids such as lauric acid, stearic acid, or oleic acid, and comprising a total number of alkoxylated units comprised between 2 and 50.

[0112] Useful emulsifiers are in particular the following products, all marketed by the Applicant:

[0113] - Soprophor® TSP / 724: a surfactant based on ethopropoxylated tri styrylphenol,

[0114] - Soprophor® 796 / P: a surfactant based on ethopropoxylated tri styrylphenol

[0115] - Soprophor® CY 8: a surfactant based on ethoxylated tri styrylphenol

[0116] - Soprophor® BSU: a surfactant based on ethoxylated tri styrylphenol

[0117] - Soprophor® S / 25: a surfactant based on ethoxylated tri styrylphenol

[0118] - Soprophor® 3D33: a surfactant based on ethoxylated tri styrylphenol phosphate

[0119] - Alkamuls® RC: a surfactant based on ethoxylated castor oil

[0120] - Alkamuls® OR / 36: a surfactant based on ethoxylated castor oil

[0121] - Alkamuls® V02003: a surfactant based on ethoxylated castor oil

[0122] - Alkamuls® OL40: a surfactant based on ethoxylated sorbitan hexaoleate

[0123] - Alkamuls® 1720: a surfactant based on ethoxylated sorbitan ester.

[0124] - Geronol® TBE724: a surfactant based on ethopropoxylated tri styrylphenol

[0125] - Geronol® TEB25: a mixture of surfactants based on ethoxylated castor oil, calcium dodecyl benzene sulfonate and alkoxylated polymers

[0126] - Rhodacal® 60 / B: a surfactant based on dodecylbenzene sulphonate

[0127] - Rhodacal® 60 / BE: a surfactant based on dodecylbenzene sulphonate.

[0128] Generally, the total amount of surfactant(s) in the agriculture formulation according to the invention, ranges from 0.05 to 40% by weight, preferentially from 0.1 to 35% by weight, more preferentially from 0.5 to 30% by weight, in particular from 1 to 25% by weight, for instance from 1 to 5% by weight, relative to the total weight of the agriculture formulation.

[0129] Generally, the total amount of anionic surfactant(s) in the agriculture formulation according to the invention, ranges from 0.05 to 40% by weight, preferentially from 0.1 to 35% by weight, more preferentially from 0.5 to 30% by weight, in particular from 1 to 25% by weight, for instance from 1 to 5% by weight, relative to the total weight of the agriculture formulation.

[0130] Generally, the total amount of non-ionic surfactant(s), in particular polyalkoxylated non-ionic surfactant(s) in the agriculture formulation according to the invention, ranges from 0.05 to 40% by weight, preferentially from 0.1 to 35% by weight, more preferentially from 0.5 to 30% by weight, in particular from 1 to 25% by weight, for instance from 1 to 5% by weight, relative to the total weight of the agriculture formulation.

[0131] The agriculture formulation according to the invention may further comprise at least one co-solvent, different from the compound of the invention.

[0132] This other solvent or co-solvent is generally selected from:

[0133] - linear or branched, saturated or unsaturated, aliphatic hydrocarbons, possibly containing a halogen -, phosphorus -, sulfur - and / or nitrogen atom and / or a functional group,

[0134] - carbocyclic or heterocyclic hydrocarbons, whether saturated, unsaturated or aromatic, possibly containing a halogen -, phosphorus -, sulfur - and / or nitrogen atom and / or a functional group,

[0135] More particularly, this co-solvent is chosen from:

[0136] - alkanes, cycloalkanes and aromatic derivatives, for example paraffins with a branched chain or straight chain such as "white oil" or decalin; mono-, di- or tri alkyl benzenes or naphthalenes, the compounds sold under the name Solvesso® 100, 150, 200 standard and ND grades;

[0137] - aliphatic, cycloaliphatic or aromatic mono-, di- or tri-esters, for example alkyl alkanoates such as methyl oleate ; benzyl alkanoates; alkyl benzoates; gamma butyrolactone; caprolactone ; esters of glycerol and citric acid ; alkyl salicylates; phthalates; dibenzoates; acetoacetates; glycol ether acetates, dipropylene glycol diacetate;

[0138] - alkyl mono-, di-, or tri-phosphates such as for example triethyl phosphate; tributyl phosphate; or tri-2-ethylhexylphosphate;

[0139] - aliphatic, cycloaliphatic or aromatic ketones such as for example dialkyl ketones; benzyl ketones; fenchone; actetophenone; cyclohexanone; alkyl cyclohexanones;

[0140] - aliphatic, cycloaliphatic or aromatic alcohols such as for example glycols; 2-ethylhexanol; cyclohexanol; benzyl alcohols; tetrahydrofurfuryl alcohol;

[0141] - aliphatic, cycloaliphatic or aromatic ethers such as for example ethers of glycol, notably ethylene and propylene glycol, and their polymers; diphenyl ether, dipropylene glycol ; monomethyl or monobutyl ether, monobutyl ether of tripropylene glycol; alkoxy alkanols; dimethyl isosorbide;

[0142] - fatty acids such as for example linoleic acid, linolenic acid, oleic acid;

[0143] - carbonates such as for example propylene or butylene carbonate; lactates; fumarates, succinates, adipates, maleates;

[0144] - amides such as for example alkyldimethylamides, dimethyl- decanoamide;

[0145] - alkyl ureas;

[0146] - amines such as for example alkanolamines, morpholine ; N-alkyl- pyrrolidones;

[0147] - tetramethyl sulfone;

[0148] - dimethyl sulfoxide;

[0149] - halogenoalkanes or halogenated aromatic solvents such as for example chloroalkanes or chlorobenzene.

[0150] Crystallisation inhibitors may also be present in the agriculture formulations according to the invention. Crystallisation inhibitors may be the cosolvents mentioned here above. Crystallisation inhibitors may also be non- polyalkoxylated fatty alcohols or fatty acids, for example mention may be made of the product Alkamuls® OL700 marketed by the Applicant, alkanolamides, polymers.

[0151] The agriculture formulation according to the invention may further contain one or more additives different from the ingredients described previously, and which are preferably chosen from viscosity modifying agents, suspending agents, antifoam agents and defoamers, in particular silicone antifoams and defoamers, anti-rebound agents, anti-leaching agents, penetration adjuvants, inert fillers, in particular mineral fillers, binders, diluents, anti-freeze agents, stabilisers, dyes, emetic agents, stickers (adhesion promoters), absorbents, dispersants, disintegration agents, wetting agents, preservatives and / or anti-microbials.

[0152] Each additive can be present in the agriculture formulation according to the invention in an amount ranging from 0 to 20% by weight, preferably from 0 to 10% by weight, relative to the total weight of the agriculture formulation. Each additive can be for instance present in the agricultural formulation according to the invention in an amount ranging from 0.1 to 20% by weight, in particular from 0.1 to 10% by weight, relative to the total weight of the formulation. Each additive can be present in the agrochemical formulation according to the invention in an amount preferably ranging from 0 to 5% by weight, notably from 0.1 to 5% by weight, relative to the total weight of the formulation. A person skilled in the art will be able to choose these optional additives and their amounts so that they do not harm the properties of the agriculture formulation of the present invention.

[0153] Advantageously, the agriculture formulation according to the invention is in a liquid form, at 20°C and at atmospheric pressure (i.e., 1.013x105 Pa) and may be in the form of a concentrate of agricultural active comound(s), a diluted concentrate, or a sprayable diluted.

[0154] Different types of formulation may be used according to the different agricultural active compound(s). The formulations that it is possible to use depend on the physical form of the agricultural active materials (for example solid or liquid) and on their physicochemical properties in the presence of other compounds such as water or solvents.

[0155] For practical reasons (for example for reasons of ease of handling), it may be preferred to use formulations in liquid form. Depending on the physicochemical properties of the different agricultural active compound(s) considered, formulations can be in the form of emulsifiable concentrates (EC), concentrated emulsions in water (EW), microemulsions (ME), suspoemulsions (SE), oil dispersions (OD), dispersible concentrates (DC), suspension concentrates (SC), capsule suspensions (CS), soluble liquids (SL), flowable concentrates for seed treatments (FS).

[0156] Preferably, the agriculture formulation according to the invention is in the form of an emulsifiable concentrate (EC), concentrated emulsion in water (EW), microemulsion (ME), suspoemulsion (SE), oil dispersion (OD), dispersible concentrate (DC), capsule suspension (CS), soluble liquid (SL).

[0157] More preferentially, the agriculture formulation according to the invention is in the form of an emulsifiable concentrate, an emulsion in water concentrate, a microemulsion concentrate, a suspoemulsion concentrate, an oil dispersion concentrate or a dispersible concentrate.

[0158] In a particular embodiment, the agriculture formulation according to the invention is in the form of an emulsifiable concentrate (EC).

[0159] The agriculture formulation according to the invention is generally a concentrated agrochemical formulation and is intended to be spread out over a cultivated field or a field to be cultivated, most often after dilution with water, in order to obtain a diluted composition. Dilution is generally carried out by the farm operator, directly in a tank (“tank-mix”), for example in the tank of a device intended to spread out the composition. This does not exclude the possibility of the farm operator adding other plant-protective products, for example fungicides, herbicides, pesticides, insecticides, fertilisers, adjuvants, etc. Thus, the formulation may be used for preparing a formulation diluted in water of the agricultural active compound(s), by mixing at least one part by weight of concentrated formulation with at least 10 parts of water, preferably less than 10,000 parts. The dilution ratios and the amounts to be applied over the field generally depend on the agricultural active compound(s) and on the desirable dose for treating the field (this may be determined by the farm operator).

[0160] According to one embodiment of the invention, the agrochemical formulation according to the invention is aqueous.

[0161] According to this embodiment, the water content of the agriculture formulation preferably ranges from 5 to 99% by weight, more preferentially from 20 to 95% by weight, even more preferentially from 25 to 90% by weight, in particular from 25 to 85% by weight, for instance from 25 to 70% by weight, relative to the total weight of the agriculture formulation.

[0162] According to this embodiment, the pH preferably ranges from 1 to 11, and particularly from 2.5 to 9.5.

[0163] The pH of the formulations can be adjusted to the desired value by means of basifying agents or acidifying agents. Use may be made, among the basifying agents, of one or more alkaline agents, such as ammonia, sodium hydroxide or ethanolamine. Mention may be made, by way of examples, among the acidifying agents, of inorganic or organic acids, such as hydrochloric acid or orthophosphoric acid.

[0164] According to a particular embodiment of the invention, the agriculture formulation may advantageously comprise: a) from 0.01 to 90% by weight, preferably from 5 to 60% by weight, of at least one agricultural active compound (only one agricultural active compound or a combination of different agricultural active compounds), preferably at least one pesticide, relative to the total weight of the agriculture formulation, b) from 5 to 90% by weight, preferably from 10 to 90% by weight, in particular from 30 to 90% by weight, for instance from 30 to 80% by weight, of a compound of the invention or of a mixture of compounds according to the present invention, relative to the total weight of the agriculture formulation, c) from 0.1 to 40% by weight, preferably from 1 to 30% by weight, of at least one said co- solvent, relative to the total weight of the agriculture formulation, d) from 0.05 to 40% by weight, preferably from 0.1 to 35% by weight, more preferentially from 0.5 to 30% by weight, in particular from 1 to 25% by weight, for instance from 1 to 5% by weight, of at least one surfactant, relative to the total weight of the agriculture formulation, e) from 5 to 90% by weight, preferably from 10 to 80% by weight, in particular from 25 to 70% by weight, of water, relative to the total weight of the agriculture formulation.

[0165] Known conventional methods for preparing agriculture formulations may be implemented. It is possible to undertake this by simply mixing the constituents.

[0166] The agriculture formulation according to the invention may be used to kill or inhibit pests and / or clean and / or inhibit growth of undesired plants.

[0167] The agriculture formulation according to the invention can be diluted and applied to at least one plant, area adjacent to a plant, soil adapted to support growth of a plant, root of a plant, foliage of a plant, and / or seed adapted to produce a plant, in a customary manner; for example by watering (drenching), drip irrigation, spraying, and / or atomizing.

[0168] In the above description, all the preferred embodiments with regard to the components may be used individually or in combination.

[0169] The compound of the present invention is also useful for other coating applications, the manufacturing of membranes, or solid batteries. It can also be used as a solvent in recycling processes of polymers, especially chemically resistant polymers like PVDF or PVDC (polyvinylidene chloride), still as a replacement of polar solvents such as NMP, DMF, DMSO, acetophenone and DMAc. It can also been used for the preparation, in solution, of polycondensates, especially polyimides or polyesters or polyamides or polyamide-imides, especially partially or completely aromatic polycondensates such as aromatic polyamides (aramids). Finally, it can also be used as cleaning solvent for the cleaning of equipment like reactors for instance, in particular polymerization reactors. Since the compounds of the invention are advantageously eco-friendly solvents and have preferably good safety and sustainable profiles, they can also advantageously be used as solvents in household care formulations, used in homes or in public areas (hotels, offices, factories, etc.). They may be formulations for cleaning hard surfaces such as floors, the surfaces of furniture and of kitchen and bathroom fittings, or dishes. These formulations may also be used in the industrial sphere for degreasing manufactured products and / or for cleaning them.

[0170] EXAMPLES

[0171] All the reactions in Examples 1 to 3 have been conducted in carefully dried vessels and under an inert nitrogen atmosphere. All the reactants were used as such without any further purification unless otherwise indicated.

[0172] Example 1

[0173] Synthesis of (la)

[0174] In a IL double-jacketed reactor equipped with a mechanical stirrer (four inclined plows glass stirring device), baffles, a condenser (10°C) and a temperature probe are added at room temperature:

[0175] - 100 g of tetrahydrofurfuryl alcohol (THFA, 94.88 mL, 0.98 mole, 1 eq.).

[0176] - 97.1 g of N,N-dimethylacrylamide (100.9 mL, 0.98 mole, 1 eq.).

[0177] The homogeneous mixture is then allowed to stir (900 rpm) at room temperature and 0.530 g of sodium methylate (0.01 mole, 1 mol%) is added to the reaction solution in one shot.

[0178] The reaction mixture is then allowed to stir at 5°C and the reaction progress is followed up over time thanks toJH NMR analysis.

[0179] After 2h00 stirring at 5°C, the conversion level is only 5%. The reaction mixture is then allowed to warm up at room temperature (25°C) and is stirred at this temperature during 16h00. At this stage the conversion level reaches 88% which is the maximum level of conversion that can be attained at room temperature under those conditions due to an equilibrated reaction.

[0180] The base catalyst is then neutralized by the careful addition at 25°C of 1.14 g of a H3PO4 85 wt. % aqueous solution (0.0099 mole, 0.99 eq. with respect to NaOMe) in order to reach 6.5 < pH < 7.5 (measured at 25°C after 10% dilution of the crude in water). In that case the final pH after neutralization was 6.9.

[0181] The unconverted reactants (THFA and N,N-dimethylacrylamide) as well as water and traces of methanol are then distilled off under vacuum (doublejacket temperature set up at 150-170 °C, 6 mbar).

[0182] During the distillation, precipitation of the inorganic phosphate salts is observed.

[0183] After distillation, 131.5 g of a yellow-orange crude is obtained along with 47.2 g for the collected distillate (containing 44 wt. % of the desired GSA-2 product, 32 wt. % of THFA and 23 wt. % of N,N-dimethylacrylamide according to1H NMR).

[0184] The crude is then allowed to cool down at room temperature and the sodium phosphate salts are removed through filtration over a silica plug using ethyl acetate (2L) as the eluant.

[0185] The ethyl acetate solvent is then removed under vacuum (95°C, 2 mbar) in order to obtain 120.8 g of GSA-2 (> 99 wt. % purity, acid value = 0 mg(KOH) / g and water content = 20 ppm H2O Karl-Fischer) corresponding to a yield of 61% (loss of product in the distillate that can be recovered).

[0186] 'H NMR (CDCI3, 400 MHz) 5 (ppm): 3.85-3.74 (m, 1H), 3.68-3.46 (m, 4H), 3.28-3.18 (m, 2H), 2.80 (s, 3H), 2.71 (s, 3H), 2.48-2.34 (m, 2H), 1.76-1.56 (m, 3H), 1.40-1.30 (m, 1H).

[0187] 13C NMR (CDCI3, 101 MHz) 5 (ppm): 170.59, 77.51, 73.62, 67.98,

[0188] 67.38, 37.02, 34.93, 33.43, 27.72, 25.34. Example 2

[0189] Synthesis of

[0190] In a IL double-jacketed reactor equipped with a mechanical stirrer (four inclined plows glass stirring device), baffles, a condenser (12°C) and a temperature probe are added at room temperature:

[0191] - 150 g of solketal (140 mL, 1.14 moles, 1 eq.).

[0192] - 112.5 g of N,N-dimethylacrylamide (117 mL, 1.14 moles, 1 eq.).

[0193] The homogeneous mixture is then allowed to stir (550 rpm) at room temperature and 0.670 g of sodium methylate (0.012 mole, 1 mol%) is added to the reaction solution in one shot.

[0194] The reaction mixture is then allowed to stir at 10°C and the reaction progress is followed up over time thanks toJH NMR analysis.

[0195] After 2h00 stirring at 10°C, the conversion level is only 2%. The reaction mixture is then allowed to warm up at room temperature (25°C) and is stirred at this temperature during 17h30.

[0196] At this stage the conversion level reaches 88% which is the maximum level of conversion that can be attained at room temperature under those conditions due to an equilibrated reaction. In order to confirm this fact, an additional amount of sodium methylate is added to the reaction mixture (0.670 g, 0.012 mole, 1 mol% additional amount) and the mixture is allowed to stir for an additional hour at 25 °C.JH NMR analysis revealed that this catalyst addition did not result to any conversion improvement.

[0197] The base catalyst is then neutralized by the careful addition at 25°C of 1.60 g of a H3PO4 85 wt. % aqueous solution (0.014 mole, 0.6 eq. with respect to NaOMe) in order to reach 7 < pH < 8 (measured at 25°C after 10% dilution of the crude in water). In that case the final pH after neutralization was 7.8.

[0198] The unconverted reactants (solketal and N,N-dimethylacrylamide) as well as water and traces of methanol are then distilled off under vacuum (doublejacket temperature set up at 170 °C, 8 mbar).

[0199] During the distillation, precipitation of the inorganic phosphate salts is observed. After distillation, 218.5 g of a yellow-orange crude is obtained along with 48.37 g for the collected distillate (containing 56 wt. % of solketal and 44 wt. % of N,N-dimethylacrylamide according to ’H NMR)

[0200] The crude is then allowed to cool down at room temperature and the salts are removed through filtration over a silica plug using ethyl acetate (2L) as the eluant containing 0.1 wt. % of triethylamine.

[0201] The solvent is then removed under vacuum (95°C, 2 mbar) in order to obtain 205.6 g of GSA-14 (98 wt. % purity, acid value = 0 mg(KOH) / g and water content = 650 ppm H2O Karl-Fischer) corresponding to a yield of 78%.

[0202] ‘H NMR (CDCI3, 400 MHz) 5 (ppm): 4.17 (quin, 1H, J = 6.0 Hz), 3.94 (dd, 1H, J = 8.1 Hz, 6.5 Hz), 3.72 (t, 2H, J = 6.8 Hz), 3.60 (dd, 1H, J = 8.1, 6.5 Hz), 3.46 (dd, 1H, J = 10.2, 5.9 Hz), 3.40 (dd, 1H, J = 10.2, 5.9 Hz), 2.92 (s, 3H), 2.85 (s, 3H), 2.53 (t, 2H, J = 6.8 Hz), 1.32 (s, 3H), 1.26 (s, 3H).

[0203] 13C NMR (CDCI3, 101 MHz) 5 (ppm): 170.79, 109,44, 74.72, 72.30, 67.86, 66.70, 37.32, 35.31, 33.64, 26.80, 25.45.

[0204] Example 3

[0205] Synthesis of (Ic) and (Id) mixture

[0206] In a IL double-jacketed reactor equipped with a mechanical stirrer (four inclined plows glass stirring device), baffles, a condenser (10°C) and a temperature probe are added at room temperature:

[0207] - 256.4 g of glycerol formal (213 mL, 2.46 moles, 1 eq., composed of 39 wt. % of the 1,3-dioxolane isomer and 61 wt. % of the 1,3-dioxane isomer) which has been dried over molecular sieve prior to the reaction.

[0208] - 95.2 g of N,N-dimethylacrylamide (99 mL, 0.96 mole, 0.39 eq.).

[0209] The homogeneous mixture is then allowed to stir (400 rpm) at room temperature and 0.624 g of sodium methylate (0.01 mole, 0.45 mol% with respect to glycerol formal) is added to the reaction solution in one shot. An exothermy is observed with the temperature raising to 48°C, the reaction mass is allowed to cool down at 10°C and the reaction progress is followed up over time thanks to1H NMR analysis. After 4h00 stirring at 10°C, no conversion is observed. The reaction mixture is then allowed to warm up at room temperature (25°C) and 7.6 g of sodium methylate is again added to the reaction mass (0.14 mole, 5.7 mol% with respect to glycerol formal) in one shot. The mixture is allowed to stir at 25°C during 24h00.

[0210] At this stage the conversion level of N,N-dimethylacrylamide reaches 51% and the analysis shows that under those conditions both glycerol formal isomers are reactive.

[0211] Therefore, an additional amount of N,N-dimethylacrylamide (149.2 g, 155 mL, 1.51 moles, 0.61 eq.) is added to the reaction mixture in one shot followed by an additional amount of sodium methylate (2.86 g, 0.05 mole, 2.2 mol% wrt. glycerol formal).

[0212] The mixture is allowed to stir for an additional 67h00 at 25°C.

[0213] JH NMR analysis revealed that at this stage that the conversion level reached 80%.

[0214] The base catalyst is then neutralized by the careful addition at 25°C of 16.5 g of a H3PO4 85 wt. % aqueous solution (0.14 mole, 0.72 eq. with respect to total NaOMe) in order to reach 7 < pH < 8 (measured at 25°C after 10% dilution of the crude in water). As the pH obtained after H3PO4 addition was too low, 12.4 g NaOH (35 wt. %) was then added to correct the pH at a level above 7 (in that case pH was measured at 7.2).

[0215] The unconverted reactants (glycerol formal and N,N-dimethylacrylamide) as well as water and traces of methanol are then distilled off under vacuum (double-jacket temperature set up at 170 °C, 17 mbar).

[0216] After distillation, 371.33 g of a yellow-orange crude is obtained along with 134.57 g for the collected distillate (which contains 53 wt. % of glycerol formal, 39 wt. % of N,N-dimethylacrylamide and 8 wt. % of N,N-dimethyl-3- methoxypropionamide according to1H NMR)

[0217] The crude is then allowed to cool down at room temperature and the salts are removed through filtration over a silica plug using ethyl acetate (2L) as the eluant. The solvent is then removed under vacuum (95°C, 24 mbar) in order to obtain 320.6 g of GSA-17 (47.4 wt. % 1,3-dioxolane derivative, 50.2 wt. % 1,3- dioxane derivative, 0.05 wt. % N,N-dimethylacrylamide, 2.1 wt. % N,N- dimethyl-3 -methoxypropionamide, 0.2 wt. % AcOEt, acid value = 5.1 mg KOH / g and water content = 0.11 wt. % H2O Karl-Fischer) corresponding to a yield of 80%.

[0218] 'H NMR (CD3OD, 400 MHz) 5 (ppm):

[0219] 1.3-dioxolane isomer: 4.94 (s, 1H), 4.82 (s, 1H), 4.19-4.11 (m, 1H), 3.92 (dd, 1H, J = 8.1 Hz, 6.9 Hz), 3.80 (t, 2H, J = 6.3 Hz), 3.64 (dd, 1H, J = 8.1, 5.9 Hz), 3.56-3.47 (m, 2H), 3.08 (s, 3H), 2.94 (s, 3H), 2.64 (t, 2H, J = 6.3 Hz).

[0220] 1.3-dioxane isomer: 4.81 (d, 1H, J = 6.2 Hz), 4.69 (d, 1H, J = 6.2 Hz), 4.02 (dd, 2H, J = 11.6 Hz, 3.4 Hz), 3.77 (t, 2H, J = 6.3 Hz), 3.68 (dd, 2H, J = 11.6 Hz, 6.0 Hz), 3.45-3.30 (m, 1H), 3.08 (s, 3H), 2.94 (s, 3H), 2.64 (t, 2H, J = 6.3 Hz).

[0221] 13C NMR (CD3OD, 101 MHz) 5 (ppm), both isomers: 173.64, 173.52, 96.20, 94.65, 75.86, 72.57, 71.97, 70.26, 68.89, 67.89, 66.49, 38.09, 38.05, 35.87, 34.79, 34.56.

[0222] Example 4

[0223] Solubility test with different mono-fungicides

[0224] In Example 4, solubility tests with different mono-fungicides (active ingredients) have been carried out. For this purpose, the solubility of the test fungicides was assessed in the solvents prepared in Examples 1 to 3 at different concentrations and at three different temperatures / conditions: 25°C, 0°C and 0°C + seeding in order to determine the maximum solubility of the active ingredient in the solvent system at a given temperature.

[0225] The solutions were monitored for 1 week to watch for any crystallization of the active ingredient over ageing. Mixtures were prepared by solubilizing the active ingredient at a certain concentration in a solvent system (pure). Each active ingredient was individually weighted and added to the solvent system. The mixture was stirred at 60 rpm using a rotator drive during 24 h at room temperature. The solubilizing capabilities of each system was based on visual observations at room temperature, 0°C (1 week), and 0°C after seeding (1 week). Seeding corresponds to the addition of the smallest possible crystal of each active ingredient in the solution. It is performed in order to avoid supersaturation of actives ingredient. Addition of a crystal brings the sample back to the thermodynamical stability.

[0226] If at a given concentration and temperature, the mixture is limpid (L) (homogeneous liquid phase), the active ingredient is considered to be soluble in a solvent at this concentration and temperature. However, if a turbid solution (T), crystals (C), suspended particles, or deposit (D) appears, the active ingredient is not soluble anymore in a solvent and the maximum solubility has been reached. The maximum solubility is defined as the maximum amount of active ingredient(s) that can be dissolved in the solvent system, equal to the amount at which the mixture remains limpid. The higher the active ingredient concentration in a solvent is, the more efficient the solvent is for the solubilization of this active ingredient.

[0227] Table 1 shows the maximum solubility (% w / v (X% = X g of active ingredient in 100 mL of solution (i.e. for 90 mL of solvent))) of different monofungicides (active ingredients) in the solvents prepared in Examples 1 to 3 at room temperature (25°C), 0°C (1 week) and 0°C after seeding (1 week).

[0228] It can be seen from Table 1 that the solvents prepared in Examples 1 to 3 are efficient solvents for achieving high maximum solubilities of different monofungicides.

[0229] It can furthermore be seen from Table 1 that the solvents prepared in Examples 1 to 3 have similar and even better solubility performance with respect to the fungicides tested than Cyrene® (Dihydrolevoglucosenone) and Rhodiasolv® ADMA 10 (N,N-dimethyldecanamide).

[0230] Example 5

[0231] Solubility test with different combo-fungicides

[0232] In Example 5, solubility tests analogously to Example 4 have been carried in order to assess the solubility of different combinations of fungicides in the solvent prepared in Example 1 at different concentrations and at three different temperatures / conditions: room temperature (25°C), 0°C and 0°C + seeding.

[0233] Table 2 shows the solubility of different combinations of fungicides in the solvent prepared in Example 1.

[0234] It can be seen from Table 2 that the solvent prepared in Example 1 is an efficient solvent for combinational fungicide formulations.

[0235] It can furthermore be seen from Table 2 that the solvent prepared in Example 1 has a better solubility performance with respect to fungicide combinations than NBP (l-Butylpyrrolidon-2-one), Cyrene® and Rhodiasolv® ADMA10.

[0236] Example 6

[0237] Solubility test with different urease and nitrification inhibitor actives

[0238] In Example 6, solubility tests analogously to Example 4 have been carried out in order to assess the solubility of different urease and nitrification inhibitors (NBPT = N-(n-butyl)thiophosphoric triamide; DCD = dicyandiamide) in the solvent prepared in Example 1 at different temperatures / conditions: 25°C, -5°C (1 week).

[0239] Table 3 shows the maximum solubility (% w / v) of NBPT and DCD in the solvent prepared in Example 1 at room temperature and at -5°C (1 week).

[0240] It can be seen from Table 3 that the solvent prepared in Example 1 is an efficient solvent for achieving high maximum solubility in particular for NBPT.

[0241] It can furthermore be seen from Table 3 that the solvent prepared in Example 1 has a better solubility performance with respect to DCD than NBP and Cyrene®.

[0242] NBP / NBPT formulation shows a color change at -5°C , which is undesirable. Cyrene® / NBPT formulation shows high viscosity at -5°C, which is also undesirable. Example 7

[0243] Solubility test with a combination of different urease and nitrification inhibitor actives

[0244] In Example 7, solubility tests analogously to Example 4 have been carried in order to assess the solubility of a combination of NBPT and DCD in the solvent prepared in Example 1 at different temperatures / conditions: 25°C, -5°C (1 week).

[0245] Table 4 shows the solubility of the NBT / DCD combination in the solvent prepared in Example 1. It can be seen from Table 4 that the solvent prepared in Example 1 has a better solubility performance with respect to the combination of NBPT and DCD (20 / 10 % w / v) than NBP and Cyrene®. Both NBP and Cyrene® are not good solvents for the NBPT / DCD combination.

[0246] Table 1

[0247] Table 2

[0248] L = limpid mixture; C = crystal formation; No = no dissolution

[0249] Table 3

[0250] No = no dissolution

[0251] Table 4

[0252] L = limpid mixture; No = no dissolution

Claims

C L A I M S1. A compound of formula (I)whereinR1and R2are independently selected from -(Ci-Ce)alkyl including - (Ci)alkyl, -(C2)alkyl, -(Cs)alkyl, -(C4)alkyl, -(Cs)alkyl, and -(Ce)alkyl, or R1and R2form with the nitrogen atom a heterocycle containing 4 to 8 carbon atoms;R3is a residue of formula (Ila) or formula (lib)whereinX is -CH2- or -O-; andR4is hydrogen or -(Ci-C4)alkyl including -(Ci)alkyl, -(C2)alkyl, -(C3)alkyl, -(C4)alkyl.

2. The compound according to claim 1, wherein R1and R2are independently selected from -(Ci-C3)alkyl including -(Ci)alkyl, -(C2)alkyl, -(C3)alkyl.

3. The compound according to claim 1 or claim 2, wherein R1and R2is methyl.

4. The compound according to any one of claims 1 to 3, wherein R4is hydrogen or methyl.

5. The compound according to any one of claims 1 to 4, wherein R3is a residue of formula (Ila), X = -CH2- and R4= H; or R3is a residue of formula (Ila), X = -O- and R4= methyl; or R3is a residue of formula (Ila), X = -O- and R4= H; or R3is a residue of formula (lib), X = - O- and R4= H; or R3is a residue of formula (lib), X =-O- and R4= methyl.

6. The compound according to any one of claims 1 to 5, wherein R1= R2= methyl, R3is a residue of formula (Ila), X = -CH2- and R4= H; or R1= R2= methyl, R3is a residue of formula (Ila), X = -O- and R4= methyl; or R1= R2= methyl, R3is a residue of formula (Ila), X = -O- and R4= H; or R1= R2= methyl, R3is a residue of formula (lib), X = -O- and R4= H; or R1= R2= methyl, R3is a residue of formula (lib), X = -O- and R4= methyl.

7. The compound according to any one of claims 1 to 6, wherein R1= R2= methyl, R3is a residue of formula (Ila), X = -CH2- and R4= H8. A method for the production of a compound according to any one of claims 1 to 7, comprising the step of reacting an alcohol R3-H and a compound of the following formula (III)wherein R1, R2and R3are defined as in claims 1 to 7, in the presence of a catalytic amount of a base.

9. Method according to claim 8, wherein the base is sodium methylate (NaOMe).

10. A composition or formulation comprising a compound according to any one of claims 1 to 7, or a mixture of compounds according to any one of claims 1 to 7.

11. An agriculture formulation comprising: a) at least one agricultural active coumpound, preferably at least one pesticide, b) a compound according to any one of claims 1 to 7 or a mixture of compounds according to any one of claims 1 to 7, c) optionally at least one emulsifier or / and one surfactant, and d) optionally water.

12. An agriculture formulation comprising: a) from 0.01 to 90% by weight, preferably from 5 to 60% by weight, of at least one agricultural active compound, preferably at least one pesticide, relative to the total weight of the agriculture formulationb) from 5 to 90% by weight, preferably from 10 to 90% by weight, in particular from 30 to 90% by weight, for instance from 30 to 80% by weight, of a compound according to any one of claims 1 to 7 or of a mixture of compounds according to any one of claims 1 to 7, relative to the total weight of the agriculture formulation c) from 0.1 to 40% by weight, preferably from 1 to 30% by weight, of at least one said co-solvent, relative to the total weight of the agriculture formulation, d) from 0.05 to 40% by weight, preferably from 0.1 to 35% by weight, more preferentially from 0.5 to 30% by weight, in particular from 1 to 25% by weight, for instance from 1 to 5% by weight, of at least one surfactant, relative to the total weight of the agriculture formulation, and e) from 5 to 90% by weight, preferably from 10 to 80% by weight, in particular from 25 to 70% by weight, of water, relative to the total weight of the agriculture formulation.

13. Use of the compound according to any one of claims 1 to 7 as a solvent, cosolvent and / or crystallization inhibitor, in particular in agriculture formulations comprising an active ingredient and in fertilizer formulations comprising a fertilizer and / or a fertilizer stabilizer, in particular a nitrogen fertilizer and / or a nitrogen fertilizer stabilizer and / or a urease or nitrification inhibitor.

14. Use according to claim 13 for the solubilization of an active ingredient in an agriculture formulation.

15. Use according to claim 14, wherein the active ingredient is a pesticide, preferably selected from the group consisting of a herbicide, an insecticide, an acaricide, a fungicide, algicide, a molluscicide, a miticide, a nematicide, a biocide and a rodenticide and mixtures thereof.

16. Use according to claim 13 for the solubilization of a urease or nitrification inhibitor in a fertilizer formulation, preferably an enhanced efficiency fertilizer formulation.

17. Use according to claim 16, wherein the urease or nitrification inhibitor is selected from the group consisting of N-(n-butyl)thiophosphoric triamide (NBPT) and dicyandiamide (DCD), and mixtures thereof.

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