New bio-based esteramide mixture and its use as solvent

Abstract

The present invention relates to a new bio-based esteramide mixture and its use as solvent, more particularly as a polar aprotic solvent e.g. for the solubilization of agricultural active agents in agriculture formulations.

Description

[0001] New bio-based esteramide mixture and its use as solvent

[0002] This application claims priority to the application filed on 22 November 2023 in Europe with Nr. 23307027.5, the whole content of this application being incorporated herein by reference for all purposes.

[0003] TECHNICAL FIELD

[0004] The present invention relates to a new bio-based esteramide mixture and its use as solvent, more particularly as a polar aprotic solvent e.g. for the solubilization of agricultural active agents in agriculture formulations.

[0005] TECHNICAL BACKGROUND

[0006] 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.

[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”. 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.

[0009] 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 filed.

[0010] 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.

[0011] In the field of emulsifiable concentrate formulations (EC), there is a need for polar aprotic solvents that are suitable to solubilize some key active ingredients at high concentrations. N-methyl-2-pyrrolidone (NMP) or N,N- dimethylacetamide are very common polar aprotic solvents that could be used for such application. However, due to their bad toxicological profile they are no longer used, and alternatives are sought.

[0012] US 8,735,324 relates to the use, as solvents, of compounds of the esteramide type.

[0013] One common esteramide compound that is used as solvent is Rhodiasolv® PolarClean which is Methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (C9H17NO3, CAS N° 1174627-68-9) and which displays a good solubility profile and good toxicity / ecotoxicity profile. However, it is not bio-sourced and there is still a need for molecules with improved solubility performance versus some compounds.

[0014] Without being bound by any theory it is believed that the presence of the ester function in the PolarClean solvent is playing a key role in the very good toxicity and ecotoxicity profile of the molecule, acting therefor as a “detoxifying” moiety. On the contrary and as already mentioned above, N,N- dimethyl acetamide for example, lacking such ester function is a well known reprotoxicant.

[0015] It is accordingly the object of the present invention to provide a polar aprotic solvent that is bio-sourced and shows improved solubilization efficiency for a wide range of agricultural active compounds.

[0016] SUMMARY OF THE INVENTION

[0017] The present invention concerns a mixture comprising compounds of the structure (Illa) and compounds of the structure (IITb), and optionally a diamide compound having the formula and structure (IIIc) : and optionally a diester compound having the formula (II):

[0018] This esteramide mixture of the invention can be synthesized by amidification of dimethyl 2-methyl succinate (DMMS) of formula (II). DMMS in turn can be obtained by hydrogenation of dimethyl itaconate, which in turn can be obtained by esterification of itaconic acid with methanol.

[0019] Hence, in a further aspect, the present invention concerns a process for manufacturing the new esteramide mixture involving at least one of the steps mentioned above. In still a further aspect, the present invention concerns the use of the new esteramide mixture as solvent, e.g. for the solubilization of agricultural active agents in agriculture formulations. The solvent of the present invention (which is new) has a very similar structure compared to PolarClean; however it presents the following advantages:

[0020] 1. It can be 100% bio-based contributing therefor to reduce the overall CO2 footprint of formulations based thereon.

[0021] 2. Importantly, despite having a similar structure than PolarClean, it shows improved solvency performances for several active ingredients, notably azoxystrobin, difenoconazole and trifloxystrobin.

[0022] Preferred embodiments of the aspects of the present invention are set out in the following description and the appended claims.

[0023] DETAILED DESCRIPTION OF THE INVENTION

[0024] The following definitions are relevant in connection with the embodiments of the present invention.

[0025] 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 formulation specified by “consisting of’.

[0026] 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.

[0027] The term “solvent” as used herein denotes a compound that is liquid at the usage temperature, preferably room temperature, and contributes to the solubilisation of a solid substance or to preventing / retarding the solidification or crystallisation of a substance from the solubilized form.

[0028] The term "room temperature" as used herein refers to a temperature of 20 to 30°C, typically to a temperature of 25 °C.

[0029] 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.

[0030] 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-m ethyl pyrimidine), ASU (l-amide-2-thiourea), TZ (lH-l,2,4-triazole), 3,4-dimethylpyrazole succinic acid (DMPSA). Non-limiting examples of urease inhibitors comprise NBPT, NPPT and CNPT (N-cyclohexylphosphoric triamide).

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

[0032] The term “% w / v“ refers to the weight amount of the respective ingredient based on a total volume of the formulation.

[0033] 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 mixture, the method, the formulation as well as the use of the mixture.

[0034] In one embodiment, the invention relates to a mixture comprising compounds of structure (Illa) and (Illb) since these are isomers which are generally obtained concomitantly when synthesizing the esteramide compound of formula CsHisNCE. Both isomers are obtained according to a parallel reactions process from the diester precursor (II) and (Illa) is the major isomer while (Illb) is the minor one. The ratio of those isomers will depend on several parameters especially the temperature employed during the amidification reaction. In some embodiments, the mixture may additionally comprise the diamide compound of structure (IIIc), since this one can also be generated as a by-product when synthesizing the esteramide of the invention. In some embodiments, the mixture may additionally comprise the diester compound precursor of structure (II) which is used for the manufacturing process of the esteramide compound of formula CsHisNCh by amidification. The residual amounts of diamide (IIIc) and diester (II) in the mixture are correlated as the diamide (IIIc) is a by-product formed by the consecutive amidation side-reaction of the esteramide (Illa) and / or (Illb). Therefore, in case of uncomplete conversion of diester (II) to the esteramide (Illa) / (Illb), the amount of diamide (IIIc) will be limited whereas residual diester (II) will be present in the mixture. On the contrary at nearly complete conversion of diester (II) resulting therefor to very limited amount of (II) in the mixture, the diamide (IIIc) will be present in higher amounts.

[0035] The above mixtures generally comprise from 75 to 95 wt% of esteramide (Illa), from 5 to 15 wt% of esteramide (Illb), from 0 to 8 wt% of diester precursor (II) and from 0 to 8 wt% of di ami de (IIIc).

[0036] The present invention also concerns a process for the manufacture of the esteramide mixture of the invention, said process comprising a step of amidification of dimethyl 2-methylsuccinate (DMMS) (II). The amidification uses dimethylamine (DMA) as reactant, and is preferably catalysed by a strong base such as for example alkali metal alkoxide or alkali metal amide or alkali metal hydroxide. Preferred examples of catalysts are: sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium / c / V-butoxide, potassium / c / V-butoxide, lithium tert- butoxide, sodium amide, lithium amide, potassium amide, lithium diisopropylamide, sodium diisopropylamide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, sodium hydroxide, lithium hydroxide, potassium hydroxide. The amidification reaction is preferably catalysed by sodium methoxide (MeONa) as described in US 8,735,324 mentioned above.

[0037] The amidification reaction is preferably conducted without any solvent, by previously condensing the required quantity of DMA gas directly in the diester precursor (II) at low temperature (for example between 0°C to 10°C) or alternatively a solvent can be used for the reaction. In that case as preferred solvents one can mention methanol, ethanol, isopropanol, THF, Me-THF. . .

[0038] DMA:(II) molar ratios can range from 0.8: 1 to 2: 1 and stoichiometric ratios are usually preferred. The amidification reaction is usually conducted at atmospheric pressure (1 atm.) but can also be conducted at higher pressure in an autoclave, for example up to 10 bar pressure. The reaction is preferably conducted at a temperature ranging between 25°C to 80°C, preferably between 40°C and 60°C. The amount of catalyst used for this reaction is preferably comprised between 0.5 to 15 mol% with respect to the diester precursor (II) and more preferably between 2 to 10 mol%. During the reaction an equimolar amount of methanol is formed as a by-product which can be separated later in the process and valorized.

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

[0040] In a preferred sub-embodiment, the process of the invention comprises an additional step of synthesizing dimethyl itaconate (DMI) by esterification of itaconic acid (IA) with methanol, preferably using standard acid catalysis, preferably with methanesulfonic acid, and / or in the presence of a polymerization inhibitor, preferably hydroquinone. As alternative suitable catalysts, one can mention other Bronsted acids such as: sulfuric acid (H2SO4), para- toluenesulfonic acid (APTS), camphorsulfonic acid, triflic acid, HC1, HBr, HI. . . Solid heterogeneous acid catalysts are also suitable for this reaction and one can mention as preferred catalysts: Amberlyst resins, acidic zeolites, Nafion, Aquivion etc. . . The esterification reaction is preferably conducted in the absence of additional solvents but alternatively a solvent can be used during this reaction. Preferred solvents are the ones able to form an azeotrope with water which is coproduced during the reaction, helping therefor its removal from the reaction media and displacing consequently the reaction equilibrium toward the formation of the ester product. The solvent free of water can then be recycled back into the reaction vessel after decantation, using for example a so called Dean-Stark equipment. As preferred solvents one can mention for example: toluene, xylene, cyclohexane, methylcyclohexane, anisole . . . When conducted in the absence of additional solvents, methanol is preferably added progressively into the reaction mixture through a fed-batch implementation. In that case under those reaction conditions, part of the added methanol is flashed out from the reaction media along with water helping to displace the reaction equilibrium. Methanol and water can then be separated through distillation and unreacted methanol can be recycled back into the esterification medium. The preferred range for the esterification reaction temperature is between 60°C and 130°C, more preferably between 90°C and 120°C. The reaction can be conducted at 1 atm. but alternatively a slight vacuum can be employed to assist water removal to improve the reaction conversion. In that case the pressure can range between 200 mbar and 1 atm. As itaconic acid and its esters are monomers, it is preferable to use during the reaction a polymerization inhibitor to avoid polymerization side reactions. As examples of preferred polymerization inhibitors once can mention: hydroquinone (HQ), para-methoxyphenol (PMP), 4 -tert-butyl catechol (TBC), phenothiazine (PTZ) etc. . . HQ and PMP are particularly preferred polymerization inhibitors in that case.

[0041] The above described process generally generates a mixture of compounds of structure (Illa) and (Illb) and optionally compounds of structure (IIIc) and / or (II), the predominant specie generally being the compound of structure (Illa).

[0042] A process incorporating several preferred embodiments of the invention is depicted in Figure 1 attached, wherein compound (I) is DMI and compound (II) is DMMS, the starting compound being itaconic acid (IA).

[0043] A process according to a preferred embodiment of the present invention namely comprises the following steps: 1. synthesizing DMI (I) by esterification of itaconic acid (IA) with methanol;

[0044] 2. synthesizing DMMS (II) by hydrogenation of DMI (I); and

[0045] 3. amidification of DMMS (II) with DMA.

[0046] Preferably, the itaconic acid used in the process of the invention is a biobased building block produced by fermentation.

[0047] In still a further embodiment, the invention concerns the use of the above esteramide mixtures as solvent, for instance in agriculture formulations.

[0048] The inventive use of the esteramide mixture of the invention as solvent also includes the use as a co-solvent and / or as a crystallization inhibitor. The use as a co-solvent implies that the esteramide mixture is used in combination with at least one further solvent. The esteramide mixture can also act as crystallization inhibitor, for example in emulsifiable concentrates, wherein the agricultural active compound is present in highly concentrated form before the concentrate is diluted in water by the farmer for its application to a field.

[0049] The esteramide mixture advantageously not only shows good to excellent solubilization properties, but also preferably very good safety and sustainable profiles, with none or very low hazard classification and none or very low ecotoxicity while still being bio-based.

[0050] The esteramide mixture may therefore generally be used 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), Rhodiasolv® PolarClean, N,N-dimethyl lactamide and Rhodiasolv® ADMA 10.

[0051] In a further aspect, the present invention relates to an agriculture formulation (or agrochemical formulation) comprising an agricultural active compound and the esteramide mixture of the invention, wherein agriculture active compounds as described above can be used.

[0052] 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 esteramide mixture used as a solvent or co-solvent; c) optionally at least one emulsifier or / and one surfactant; and d) optionally water.

[0053] 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 compounds 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.

[0054] The agricultural active compounds are generally products in pure or highly concentrated form.

[0055] The agricultural active compound suitable for use in the present invention is preferable selected from the group consisting of pesticides, biopesticides, fertilizers, fertilizer stabilizers, nutrients, biostimulants, plant growth regulators, natural plant defense enhancers, inoculants and mixtures thereof.

[0056] Pesticides suitable for use in the present invention include herbicides, insecticides, acaricides, fungicides, algicides, molluscicides, miticides, nematicides, biocides and rodenticides as well as mixtures thereof.

[0057] Non-limiting examples of fungicides suitable for use in the present invention include azoles such as e.g. prothioconazole, epoxiconazole, difenoconazole, propiconazole, cy proconazole, tebuconazole; strobilurins such as e.g. azoxystrobin, trifloxystrobin, picoxystrobin, fluoxastrobin, pyraclostrobin; and succinate dehydrogenase inhibitors (SDHIs) (carboxamides) such as bixafen, fluxapyroxad, benzovindiflupyr, fluopyram; and mixtures thereof.

[0058] Particularly good results are obtained with azoxystrobin, difenoconazole and trifloxystrobin (see the examples).

[0059] The agricultural active compounds can be water-insoluble, at 20°C and at atmospheric pressure (i.e., 1.013xl05Pa).

[0060] 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). In a further embodiment, the agriculture formulation is 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.

[0061] The fertilizer and / or fertilizer stabilizer, in particular the nitrogen fertilizer and / or nitrogen fertilizer stabilizer and / or urease and / or nitrification inhibitor may be A-(n-butyl)thiophosphoric acid triamide (NBPT) and / or dicyandiamide (DCD).

[0062] 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.

[0063] 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.

[0064] 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.

[0065] According to a particular embodiment of the invention (concentrated formulation), 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.

[0066] According to another particular embodiment of the invention (diluted formulation), 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.

[0067] Generally, the esteramide mixture 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.

[0068] It is possible to combine several agricultural active compounds in the agriculture formulation of the invention.

[0069] The agriculture formulation according to the invention may comprise at least one biostimulant.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] The agricultural formulation according to the invention may comprise at least one plant growth regulator.

[0074] 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-naphthoxyacetic 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- HC1, adenine, adenine hemisulfate, benzyladenine, kinetin, meta-topolin, N6- benzoyladenine, N- benzyl-9-(2 -tetrahydropyranyl) adenine (BPA), N-(2-chloro- 4- pyridyl)-N-phenylurea, gibberellic acid (GA3), gibberellins, gibberellins A4 + A7 (GA n), ethylene and abscisic acid.

[0075] The agriculture formulation according to the invention may optionally comprise at least one emulsifier.

[0076] 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.

[0077] 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.

[0078] Generally, the agrochemical formulation according to the invention further comprises at least one surfactant.

[0079] Advantageously, the surfactants that may be used in the invention are chosen from anionic, non-ionic, cationic, amphoteric or zwitterionic surfactants, and mixtures thereof.

[0080] Preferentially, the surfactants are chosen from anionic surfactants, nonionic surfactants, and mixtures thereof. More preferentially, the surfactants are chosen from anionic surfactants, polyalkoxylated non-ionic surfactants, and mixtures thereof.

[0081] The emulsifiers and surfactants that may be used are different from the agricultural active compound(s).

[0082] By way of examples of anionic surfactants, mention may be made without any intended limitation thereto, of:

[0083] - alkylsulfonic acids, arylsulfonic acids, optionally substituted with one or more hydrocarbon groups, and the acid function of which is partly or totally salified, like Cs-Cso alkylsulfonic acids, more particularly Cs-Cso, preferably Cio- 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,

[0084] - mono- or di-esters of sulfosuccinic 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, propoxylated, ethopropoxylated) groups,

[0085] - 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 carbon atoms, 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 propoxylated) C8-C30, preferably C10-C22 alcohol; of phosphoric acid and of a non-alkoxylated C8-C22, preferably C10-C22 alcohol,

[0086] - sulfate esters obtained from saturated or unsaturated 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 hydrocarbon 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.

[0087] 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.

[0088] By way of examples of non-ionic surfactants, mention may be made without any intended limitation thereto, of:

[0089] - 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 Ci-Ce 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- styrylphenol s, mention may be made of ethoxylated di-(phenyl-l-ethyl)phenol, containing 10 oxyethylene units ; ethoxylated di-(phenyl-l-ethyl)phenol, containing 7 oxyethylene units ; sulfated ethoxylated di-(phenyl-l-ethyl)phenol, containing 7 oxyethylene units ; ethoxylated tri-(phenyl-l-ethyl)phenol, containing 8 oxyethylene units ; ethoxylated tri-(phenyl-l-ethyl)phenol, containing 16 oxyethylene 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.

[0090] - polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated) Ce- 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.

[0091] - 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.

[0092] - sorbitan esters, optionally polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated), more particularly the cyclised sorbitol esters of C10-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.

[0093] Useful emulsifiers are in particular the following products, all marketed by the Applicant:

[0094] - Soprophor® TSP / 724: a surfactant based on ethopropoxylated tristyrylphenol,

[0095] - Soprophor® 796 / P: a surfactant based on ethopropoxylated tri styrylphenol,

[0096] - Soprophor® CY 8: a surfactant based on ethoxylated tristyrylphenol,

[0097] - Soprophor® BSU: a surfactant based on ethoxylated tristyrylphenol,

[0098] - Soprophor® S / 25: a surfactant based on ethoxylated tri styrylphenol,

[0099] - Soprophor® 3D33: a surfactant based on ethoxylated tristyrylphenol, phosphate ester,

[0100] - Alkamuls® RC: a surfactant based on ethoxylated castor oil, - Alkamuls® OR / 36: a surfactant based on ethoxylated castor oil,

[0101] - Alkamuls® V02003: a surfactant based on ethoxylated castor oil,

[0102] - Alkamuls® OL40: a surfactant based on ethoxylated sorbitan hexaoleate,

[0103] - Alkamuls® 1720: a surfactant based on ethoxylated sorbitan ester.

[0104] - Geronol® TBE724: a surfactant based on ethopropoxylated tri styrylphenol,

[0105] - Geronol® TEB25: a mixture of surfactants based on ethoxylated castor oil, calcium dodecyl benzene sulfonate and alkoxylated polymers,

[0106] - Rhodacal® 60 / B: a surfactant based on dodecylbenzene sulphonate,

[0107] - Rhodacal® 60 / BE: a surfactant based on dodecylbenzene sulphonate.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] The agriculture formulation according to the invention may further comprise at least one co-solvent, different from the esteramide mixture of the invention.

[0112] This other solvent or co-solvent can generally be selected from: - linear or branched, saturated or unsaturated, aliphatic hydrocarbons, possibly containing a halogen -, phosphorus -, sulfur - and / or nitrogen atom and / or a functional group,

[0113] - carbocyclic or heterocyclic hydrocarbons, whether saturated, unsaturated or aromatic, possibly containing a halogen -, phosphorus -, sulfur - and / or nitrogen atom and / or a functional group,

[0114] More particularly, this co-solvent is chosen from:

[0115] - 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;

[0116] - aliphatic, cycloaliphatic or aromatic mono-, di- or tri -esters, for example alkyl alkanoates such as methyl oleate ; benzyl alkanoates; alkyl benzoates; gamma butyrolactone; gamma valerolactone; caprolactone ; esters of glycerol and citric acid ; alkyl salicylates; phthalates; dibenzoates; acetoacetates; glycol ether acetates, dipropylene glycol diacetate; lactates; fumarates, succinates, adipates, maleates; levulinates;

[0117] - alkyl mono-, di-, or tri -phosphates such as for example triethyl phosphate; tributyl phosphate; or tri-2-ethylhexylphosphate;

[0118] - aliphatic, cycloaliphatic or aromatic ketones such as for example dialkyl ketones; benzyl ketones; fenchone; acetophenone; cyclohexanone; alkyl cyclohexanones; isophorone; cyclopentanone.

[0119] - aliphatic, cycloaliphatic or aromatic alcohols such as for example glycols; 2-ethylhexanol; cyclohexanol; benzyl alcohols; tetrahydrofurfuryl alcohol;

[0120] - 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; alkoxyalkanols; dimethyl isosorbide;

[0121] - fatty acids such as for example linoleic acid, linolenic acid, oleic acid;

[0122] - carbonates such as for example propylene or butylene carbonate; - amides such as for example dimethyl alkylamides, dimethyl- decanoamide; N-alkyl-pyrrolidones; dimethyl lactamide.

[0123] - alkyl ureas;

[0124] - amines such as for example alkanolamines, morpholine ;

[0125] - tetramethyl sulfone; sulfolane;

[0126] - dimethyl sulfoxide;

[0127] - halogenoalkanes or halogenated aromatic solvents such as for example chloroalkanes or chlorobenzene.

[0128] 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.

[0129] 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-microbial.

[0130] 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.

[0131] Advantageously, the agriculture formulation according to the invention is in a liquid form, at 20°C and at atmospheric pressure (i.e., 1.013xl05Pa) and may be in the form of a concentrate of agricultural active compound(s), a diluted concentrate, or a sprayable diluted.

[0132] 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.

[0133] 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).

[0134] 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).

[0135] 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.

[0136] In a particular embodiment, the agriculture formulation according to the invention is in the form of an emulsifiable concentrate (EC).

[0137] 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 formulation. 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 formulation. 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).

[0138] According to one embodiment of the invention, the agrochemical formulation according to the invention is aqueous.

[0139] 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.

[0140] According to this embodiment, the pH preferably ranges from 1 to 11, and particularly from 2.5 to 9.5.

[0141] 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.

[0142] 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 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.

[0143] Known conventional methods for preparing agriculture formulations may be implemented. It is possible to undertake this by simply mixing the constituents.

[0144] 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.

[0145] 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.

[0146] Besides their use as solvents, co-solvents and / or crystallization inhibitors, particularly in agriculture formulations, the esteramide mixtures of the invention are also useful as solvent for coating applications, the manufacturing of membranes, or solid batteries.

[0147] The esteramide mixtures of the invention can furthermore be used 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.

[0148] The esteramide mixtures of the invention can also be used as solvent 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).

[0149] Moreover, the esteramide mixtures of the invention can be used as cleaning solvent for the cleaning of equipment like reactors for instance, in particular polymerization reactors.

[0150] Since the esteramide mixtures 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 formulated 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 instance for degreasing manufactured products and / or for cleaning them.

[0151] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0152] Examples

[0153] The reactions described below were always conducted under an inert argon atmosphere.

[0154] 1. Esterification of itaconic acid (IA) with methanol to obtain DMI

[0155] The reaction was conducted in a IL double jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, a temperature probe and a distillation apparatus.

[0156] In the reactor were added:

[0157] 300 g of itaconic acid (2.31 moles). 221.6 g of dry methanol (280 mL, 6.92 moles).

[0158] 260 mg of hydroquinone (for polymerization inhibition)

[0159] 6.6 g of methanesulfonic acid (69 mmoles) as catalyst.

[0160] The reaction mixture was allowed to stir at 400 rpm and the reaction was conducted at 100-110°C (reaction mass temperature) with the progressive fed- batch addition of additional amount of methanol as during the reaction methanol was flashed out along with the water by-product allowing to displace the reaction equilibrium toward esterification completion.

[0161] Concretely, this was done by the regular addition of 666 g of methanol (841 mL, 20.8 moles) over 15h00.

[0162] After 15h00 reaction time at 100-110°C, the vessel pressure was decreased down to 600 mbar in order to achieve complete conversion toward the bis-ester.

[0163] Then the temperature was decreased down to 90°C and 11 g of Na2COs (103.5 mmoles) were added into the reaction mass at 1 atm for catalyst neutralization.

[0164] The mixture was allowed to stir at 90°C during 3h00 and 1.32 g of methanesulfonic acid were introduced into the reaction mixture.

[0165] The product was then purified through vacuum distillation (120°C in the boiler, 40 mbar pressure) to obtain the product as clear liquid.

[0166] ‘H NMR (CD3OD, 400 MHz) 5 (ppm): 6.28 (s, 1H), 5.78 (s, 1H), 3.74 (s, 3H), 3.67 (s, 3H), 3.37 (s, 2H).

[0167] 2. Catalytic hydrogenation of DMI to DMMS (II).

[0168] In a 750 mL hydrogenation autoclave reactor equipped with a Rushton turbine and baffles were successively added at room temperature:

[0169] 120 g of dimethyl itaconate (I) (0.76 mole, one half).

[0170] 261.2 mg of Pd / C (3%) (Chimet 1221L, 50% moisture).

[0171] 120 g of dimethyl itaconate (I) (0.76 mol, second half).

[0172] The autoclave was then sealed and purged three times with 10 bar of nitrogen in order to decrease the oxygen content (without stirring). Then the autoclave was purged three times with 10 bar of hydrogen (without stirring).

[0173] The mixture was then allowed to stir at 800 rpm (under 10 bar of hydrogen pressure) and the reaction mass temperature was increased to 50°C.

[0174] As soon as the slurry was stirred, the hydrogenation reaction started with hydrogen consumption and observation of exothermy (estimate of the hydrogenation reaction heat ~ 27 kcal / mol).

[0175] Reaction conversion was followed-up thanks to the hydrogen consumption showing that the hydrogenation was completed after 2h00 reaction time (50°C, 10 bar).

[0176] The reaction mixture was then allowed to cool down at room temperature under hydrogen pressure, the autoclave was decompressed and the solid catalyst was filtered out using a filtration cell (polypropylene filtration membrane 11 pm).

[0177] The product was then obtained as a transparent colorless liquid with quantitative yield and used as such for the next step.

[0178] ‘H NMR (CDC13, 400 MHz) 5 (ppm): 3.67 (s, 3H), 3.65 (s, 3H), 2.91- 2.87 (m, 1H), 2.70 (dd, 1H, J = 16.4 Hz, 8.1 Hz), 2.36 (dd, 1H, J = 16.4 Hz, 6.1 Hz), 1.17 (d, 3H, J = 7.2 Hz).

[0179] 13C NMR (CDCI3, 101 MHz) 5 (ppm): 175.57, 172. 16, 51.80, 51.58, 37.30, 35.64, 16.90.

[0180] 3. Amidification of DMMS (II) to obtain the compounds of structure Illa and Hlb

[0181] The reaction was conducted in carefully dried vessels and under an inert nitrogen atmosphere.

[0182] All the reactants were used as such without any further purification unless otherwise indicated.

[0183] DMA in methanol solutions were dried over activated molecular sieve 4A overnight prior to use (Karl-Fisher analysis confirmed that the residual water content after drying was below 600 ppm). In a IL double-jacketed reactor equipped with a mechanical stirrer (four inclined plows glass stirring device), baffles, a condenser maintained at 5°C and a temperature probe, were added at room temperature:

[0184] 94.01 g (0.587 mole) of the bis-ester intermediate (II).

[0185] 458.2 g of a solution of DMA in methanol (2M) (561.9 mL, 1.124 moles, 1.9 eq.).

[0186] The mixture was then allowed to stir at 400 rpm and 0.992 g of NaOMe (~ 3 mol% vs. (II)) catalyst were added into the reaction mixture in one shot.

[0187] The reaction mixture was then allowed to stir at 50°C (400 rpm) and the reaction progress was followed-up over time by 1H NMR analysis.

[0188] After 2h00 stirring at 50°C the conversion level was around 9%.

[0189] The reaction mixture was then allowed to stir during 16h00 at 50°C allowing to reach 35% conversion level.

[0190] 2.2 g of an additional amount of NaOMe catalyst (~ 7 mol% vs. (II)) were added into the reaction mixture in order to speed up the reaction kinetics.

[0191] The reaction mixture was then allowed to stir at 50°C (400 rpm) for an additional 24h00.

[0192] At this stage the conversion level reached 93% and the DMA in excess as well as the methanol were distilled out from the vessel (42°C in the reaction mass, 300 mbar during distillation).

[0193] The basic catalyst contained in the crude was then neutralized at room temperature through the addition of aqueous H3PO4 (85 wt%) in order to reach a final pH ~ 6.5 (measured at 10 wt% dilution in water at 25°C).

[0194] The final product was then purified through vacuum distillation.

[0195] After distillation of the residual water and methanol (coming from the catalyst neutralization) a first fraction was obtained (b.p. 75°C, 2 mbar, 4.7 g).

[0196] 1H NMR analysis shows that this fraction was mainly composed of the starting material (DMMS).

[0197] A second fraction was then collected (b.p. 122°C, 2 mbar, 54.4 g) which corresponds to the desired products (Illa and IHb).

[0198] At the end of the distillation around 37 g of solid material (heavy boilers) remained in the distillation pot.1H NMR analysis on the purified product shows that it is a mixture comprising the two following isomers in the following amounts: (Illa) = 87.1 % and (nib) = 7.1 %.

[0199] ‘H NMR (CDC13, 500 MHz) 5 (ppm) Major Isomer (Illa): 3.61 (s, 3H), 2.94 (brs, 3H), 2.94-2.85 (m, 1H), 2.85 (brs, 3H), 2.71 (dd, 1H, J = 16.6 Hz, 8.5 Hz), 2.26 (dd, 1H, J = 16.6 Hz, 5.0 Hz), 1.14 (d, 3H, J = 7.2 Hz).

[0200] 13C NMR (CDCI3, 126 MHz) 5 (ppm) Major Isomer (Illa): 176.9, 171.0, 51.9, 37.1, 36.8, 35.9, 35.5, 17.5.

[0201] ‘H NMR (CDCI3), 500 MHz) 5 (ppm) Minor Isomer (IHb): 3.55 (s, 3H), 3.2-3.1 (m, 1H), 3.03 (brs, 3H), 2.85 (brs, 3H), 1.03 (d, 3H, J = 7.0 Hz), only non-overlapping signals are indicated here.

[0202] 13C NMR (CDCI3, 126 MHz) 5 (ppm) Minor Isomer (IHb): 175.3, 173.1, 51.6, 38.0, 37.2, 35.7, 32.3, 17.4.

[0203] 4. Active ingredients solubility tests.

[0204] Solubility tests have been carried out consisting on assessing the solubility of some key strategic fungicides in the solvents of the present invention at different concentrations and respectively at room temperature (RT) and at 0°C.

[0205] The solutions were monitored during 1 week to watch for any active ingredient crystallization over ageing.

[0206] Mixtures were prepared by solubilizing an active ingredient (or combo) at a certain concentration (g / 1) in a solvent systems (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 24h 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 was performed in order to avoid supersaturation of actives ingredient. Addition of a crystal brings the sample back to the thermodynamical stability. At a given concentration, if the mixture is limpid (homogeneous liquid phase), the active ingredient is considered to be soluble in a solvent at this concentration. However, if a turbid solution, crystal, suspended particles, or deposit appears, active ingredient is not soluble anymore in a solvent and the maximal solubility is reached. The maximal 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.

[0207] The highest active ingredient concentration we can achieve in a solvent, the most efficient the solvent is for this active ingredient.

[0208] The solubility results at room temperature and at 0°C for the solvent of the present invention obtained according to example 3, and designated as GSA- 18, is shown in the tables below along with the corresponding solubility data for the solvent PolarClean taken as the reference.

[0209] As can be seen in these tables the solvent of the present invention shows higher solubility performance compared to PolarClean for: azoxystrobin, difenoconazole and trifloxystrobin.

[0210] For the other compounds, the solvent of the invention shows similar or slightly lower performances but has the advantage of being potentially biosourced.

[0211] 5. Solubility of different polymers

[0212] GSA-18 was tested as a NMP replacement as a solvent for dissolving polymers. The results are stated in the table below. As can be seen, GSA18 is a suitable replacement for the solvent NMP and can be used for the manufacturing of battery electrodes for solid-state battery or Li-ion battery or for coatings or to produce anti-fouling membranes for a wide range of filtration applications. PVDF (Solef ® grades) and Tecnoflon® are polymer binders that are usually dissolved in NMP (or DMF and DM Ac) and then used to dispense a slurry of a carbon material and the dissolved binder, also known as wet coating, onto a substrate material: the electrode.

[0213] PVDF (Solef® 1015) is also used to make micro- and ultrafiltration membranes for a wide range of filtration applications by the NIPS process (NonSolvent Induced Phase Separation). In NIPS, a polymer solution film is immersed in a non-solvent bath (water), inducing phase separation of the film into a polymer-rich phase that becomes the membrane matrix and a polymer- poor phase that becomes the membrane pores. N-methyl-2-pyrrolidone (NMP) is used as the solvents medium because it could successfully dissolve PVDF.

[0214] Polyamide-imides PAI (Tori on® grades) are used as high-performance coating materials in both automotive industry and high-end household appliances. The main need here is to find good solvents to realize the coating formulation in liquid form. NMP, DMF and DMAC are known as good solvents of such polymers.

[0215]

Claims

C L A I M S1. A mixture comprising compounds of structure (Illa) and compounds of structure (Illb), optionally a diamide compound having the formula and structure (IIIc) and optionally a diester compound of formula (II):(IIIc):

2. The mixture according to claim 1, comprising from 75 to 95 wt% of esteramide (Illa), from 5 to 15 wt% of esteramide (Illb), from 0 to 8 wt% of diester precursor (II) and from 0 to 8 wt% of di ami de (IIIc).

3. A process for the manufacture of a mixture according to claim 1 or 2, said process comprising a step of amidification of dimethyl 2-methyl succinate (DMMS, II).

4. The process according to claim 3, which uses dimethylamine (DMA), and is preferably catalysed by sodium methoxide (MeONa).

5. The process according to claim 3 or 4, which comprises an additional step of synthesizing the DMMS (II) by hydrogenation of dimethyl itaconate (DMI, I), preferably using a Pd / C catalyst.

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

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

8. Use according to claim 7 for agriculture formulations.

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

10. Use according to claim 9, wherein the agricultural active compound is a fungicide, in particular selected from azoxystrobin, difenoconazole and trifloxystrobin.

11. Use according to claim 8 for coating applications, the manufacturing of membranes, or solid batteries.

12. Use according to claim 8 in recycling processes of polymers, especially chemically resistant polymers like PVDF or PVDC (polyvinylidene chloride).

13. Use according to claim 8 for the preparation, in solution, of poly condensates, especially polyimides or polyesters or polyamides or polyamide-imides, especially partially or completely aromatic polycondensates such as aromatic polyamides (aramids).

14. Use according to claim 8 as cleaning solvent for the cleaning of equipment like reactors for instance, in particular polymerization reactors.

15. Use according to claim 8 as solvent in household care formulations, used in homes or in public areas (hotels, offices, factories, etc.), for instance formulatedfor cleaning hard surfaces such as floors, the surfaces of furniture and of kitchen and bathroom fittings, or dishes, or for use in the industrial sphere, for instance for degreasing manufactured products and / or for cleaning them.

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