New polar aprotic solvents and their synthesis

Abstract

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

Description

[0001] NEW POLAR APROTIC SOLVENTS AND THEIR SYNTHESIS

[0002] This application claims priority to European patent application N° 25315027.0 filed on 31 / 01 / 2025, the whole content of this application being incorporated herein by reference for all purposes.

[0003] TECHNICAL FIELD

[0004] The present invention relates to new polar aprotic solvents e.g. for the solubilization of agricultural active agents in agriculture formulations, and to a process for their synthesis.

[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”.In the field of Emulsifiable Concentrates (EC), there is a need for polar aprotic solvents in order to solubilize some key active ingredients at high concentrations.

[0009] Those formulations normally require using in fine a solvent or a solvents mixture that is not miscible with water in order to form a stable emulsion upon dilution in water (in the presence of a suitable emulsifier) and to avoid active ingredient crystallization (this water dilution is usually carried out by the farmer).

[0010] Globally, the most performing solvents for the solubilization of active ingredients are polar non protic solvents (e.g. Rhodiasolv® PolarClean which is Methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (C9H17NO3, CAS N° 1174627-68-9)) which are usually completely miscible with water and therefor require to be mixed with a non-water miscible non polar solvent. Mixing such polar solvent with a non-polar solvent will however reduce the solubilization power of the final solvents mixture compared to the performance obtained by the polar solvent by itself.

[0011] Therefor a better approach is to directly design a solvent that is non water miscible yet polar in order to combine within one molecule a good solubilization power and good emulsification properties.

[0012] In addition, the agriculture market is still seeking for higher performing solvents with clean toxicity / ecotoxicity profile in order to address the more and more complex active ingredients formulations which will be more and more encountered in order to face pest resistance issues.

[0013] One of the most useful solvent for the agriculture market is Rhodiasolv® ADMA-10 (N,N-dimethyl decanamide, CAS N° 14433-76-2) which can be considered as a polar non water miscible solvent.

[0014] It is an object of the present invention to provide polar aprotic solvents that:

[0015] - can be obtained through a 1 pot 2 chemical steps process starting from commodity raw materials, through a unique chemistry that makes it possible to modulate the final properties of the solvents

[0016] - display similar or better performances than Rhodiasolv® ADMA-10 - are readily biodegradable

[0017] - can be bio-sourced.

[0018] SUMMARY OF THE INVENTIONThe present invention concerns a process for the synthesis of a polar aprotic solvent, wherein said polar aprotic solvent is obtained through a transesterification reaction of aN,N-dimethyl hydroxyamide with a carboxylic or carbonic acid ester derivative of formula R-(C=O)OR” (II) where R” is an alkyl group containing between 1 and 6 carbon atoms and where R is an alkoxy group of formula (-OX’) where X’ is an alkyl group having between 1 and 6 carbon atoms or an oxoalkyl group having between 3 and 6 carbon atoms, preferably a dialkyl carbonate or an alkyl levulinate, more preferably an alkyl levulinate.

[0019] Transesterification reaction of aN,N-dimethyl hydroxyamide are known from prior art but instead of using compounds substituted with an alkoxy group or an oxoalkyl group as in the present invention, they use phenyl substituted compounds which lead to different transesterification products which are less effective as solvents, have a high melting point, can lead to odour problems and potentially show toxicity / ecotoxicity problems.

[0020] It is believed that at least some of the solvents so obtained are new.

[0021] Hence, in a further aspect, the present invention concerns a polar aprotic solvent having the generic formula (I),

[0022]

[0023] wherein

[0024] - R is an alkoxy group of formula (-OX’) where X’ is an alkyl group having between 1 and 6 carbon atoms, preferably methoxy, or an oxoalkyl group having between 3 and 6 carbon atoms, preferably 3-oxobutyl (CH3-(C=O)-CH2-CH2-); and

[0025] - R’ is an alkanediyl group selected from propane- 1,3-diyl eventually substituted by one or more C1-C3 alkyl groups, butane- 1 ,4-diyl eventually substituted by one or more C1-C3 alkyl groups, and pentane-l,5-diyl eventually substituted by one or more C1-C3 alkyl groups.

[0026] This polar aprotic solvent is biodegradable, nontoxic, safe to the environment and based on renewable raw materials, and is preferably obtained through the transesterification of a N,N-dimethyl hydroxyamide intermediate with bio-based methyl or ethyl levulinate.In still a further aspect, the present invention concerns the use of the new solvent, e.g. for the solubilization of agricultural active agents in agriculture formulations.

[0027] Preferred embodiments of the aspects of the present invention are set out in the following description and the appended claims.

[0028] DETAILED DESCRIPTION OF THE INVENTION

[0029] The following definitions are relevant in connection with the embodiments of the present invention.

[0030] 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’.

[0031] 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.

[0032] 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.

[0033] The term "room temperature" as used herein refers to a temperature of 20 to 30°C, typically to a temperature of 25°C.

[0034] 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.

[0035] 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 (1 -mercapto- 1, 2, 4-triazole), AM (2-amino-4-chloro-6-methyl pyrimidine), ASU (l-amide-2-thiourea), TZ (1H- 1,2, 4-triazole), 3,4-dimethylpyrazole succinic acid (DMPSA). Non-limiting examples of urease inhibitors comprise NBPT, NPPT and CNPT (N-cyclohexylphosphoric triamide).

[0036] The term “formulation” as used herein refers to a composition comprising at least the solvent 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).

[0037] 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 product, the method, the formulation as well as the use of the product.

[0038] The present invention concerns a process for the synthesis of a polar aprotic solvent, wherein said polar aprotic solvent is obtained through a transesterification reaction of aN,N-dimethyl hydroxyamide intermediate.

[0039] Preferably, the alcohol function in said N,N-dimethyl hydroxyamide intermediate is a primary alcohol because it leads to a higher reactivity in the transesterification reaction.

[0040] During the transesterification reaction, the N,N-dimethyl hydroxyamide intermediate is reacted with a carboxylic or carbonic acid ester derivative of formula R-(C=O)OR” (II) where R” is an alkyl group containing between 1 and 6 carbon atoms and where R has the same meaning as defined above.

[0041] During the transesterification reaction, an alcohol (R”OH) is generated as by-product.

[0042] In a preferred embodiment, the N,N-dimethyl hydroxyamide intermediate is reacted with a dialkyl carbonate or an alkyl levulinate, preferably an alkyl levulinate. Preferably, the alkyl groups in the dialkyl carbonate or alkyl levulinate are methyl or ethyl, which means that the alcohol R’ ’ is methanol or ethanol. These compounds can be synthesized from biomass and hence, can be biosourced. Good results are obtained with dimethyl carbonate or methyl or ethyl levulinate, the levulinates being preferred.The transesterification reaction is preferably conducted in a basic medium, using a base catalyst. This namely allows accelerating the reaction kinetic and reducing side reactions and hence, improving the efficiency and selectivity of the transesterification reaction. Preferred examples of base catalysts are: lithium, sodium or potassium alkoxides such as e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium / c / V-butoxide. sodium / c / v-butoxide: tertiary amines such as e.g. triethylamine, diisopropylethylamine (Hiinig base), N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), l,5-diazabicyclo[4.3.0]non-5-ene (DBN), l,4-diazabicyclo[2.2.2]octane (DABCO), heterogeneous base catalysts such as e g. MgO, CaO, K2CO3, N zCCh, NasPC , K3PO4.

[0043] The transesterification reaction is preferably catalysed by sodium methoxide (MeONa) or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0044] Preferably, the transesterification reaction is conducted in the absence of a solvent. However an additional solvent can also be used during the reaction. Preferred examples of solvents are: toluene, xylene, 2-methylTHF, THF, DMSO, cyclohexane, hexane, pentane, pyridine, acetonitrile, anisole etc... If an additional solvent is used during the trans-esterification reaction, the solvent is preferably separated after reaction completion, base catalyst neutralization and optional washing with aqueous solution through vacuum distillation in order to be recovered and recycled.

[0045] During the transesterification reaction, the generated alcohol by-product (R”OH) is preferably removed through distillation in order to displace the equilibrium toward completion. The transesterification reaction is typically conducted at a temperature ranging from 60°C to 200°C, preferably from 80°C to 170°C and even more preferably from 80°C to 140°C. In addition, the reaction can be conducted under vacuum to assist alcohol by-product removal, at a pressure ranging from 1 mbar to 1 atm., preferably from 5 mbar to 800 mbar and even more preferably from 10 mbar to 600 mbar depending on the nature of the alcohol by-product.

[0046] Alternatively, the trans-esterification equilibrium can be displaced toward the desired product by using an excess of the ester reactant (II), typically from 2 molar equivalents (with respect to the hydroxy ami de intermediate) to 10 molar equivalents, preferably from 2 molar equivalents to 8 molar equivalents and even more preferably from 3 molar equivalents to 5 molar equivalents. In that case the ester reactant acts also as the reaction solvent and the reactant excess ispreferably separated after reaction completion, base catalyst neutralisation and optional aqueous washing through vacuum distillation in order to be recycled.

[0047] In a preferred embodiment of the invention, the N,N-dimethyl hydroxyamide intermediate is obtained through a ring opening amidification of a lactone with dimethylamine.

[0048] According to this embodiment, the process of the invention comprises the following steps:

[0049] - ring opening amidification of a lactone with dimethylamine to synthesize aN,N-dimethyl hydroxy amide intermediate.

[0050] - transesterification of the N,N-dimethyl hydroxy amide intermediate with a carboxylic or carbonic acid ester derivative of formula R-(C=O)OR” (II) as described above.

[0051] In this embodiment, the lactone is preferably selected from gammalactones, delta-1 actones and epsilon-lactones. Preferably, the lactones are such that after the ring opening amidification, they lead to a primary alcohol function in the N,N-dimethyl hydroxyamide.

[0052] More preferably, the lactone is selected from gamma-butyrolactone, delta-valerolactone and epsilon- caprolactone, gamma-butyrolactone and epsilon caprolactones being particularly preferred.

[0053] The ring opening amidification reaction uses dimethylamine (DMA) as reactant, and is preferably catalysed by a strong base. As preferred strong bases one can mention lithium, sodium or potassium alkoxides such as e.g. sodium methoxide, sodium ethoxide, potassium methoxide or potassium tert-butoxide. If a strong base catalyst is used for the ring opening lactone amidification, the same catalyst is also active for the trans-esterification and no additional catalyst may be required. Alternatively, it may be necessary to add an additional quantity of base catalyst prior to the transesterification step which may be different from the catalyst used in the first lactone amidification step.

[0054] The ring opening amidification reaction may be conducted in a solvent, preferably an alcoholic solvent (e.g. MeOH, EtOH, iPrOH, n-BuOH etc... ) by progressively adding the lactone to the DMA + catalyst mixture. Since solutions of DMA in ethanol are commercially available, in a preferred embodiment, the solvent is ethanol. The combination of a strong basic catalyst with an alcoholic solvent improves the selectivity of the reaction via the formation of the desired hydroxy amide and limits the formation of the ester by-product derived from the nucleophilic attack of the alcoholic solvent on the lactone. Alternatively, thereaction can be conducted without any solvent, preferably by progressively adding the lactone into condensed DMA, preferably at a temperature ranging from -10°C to 5°C.

[0055] As already mentioned, in a preferred embodiment, when both the transesterification reaction and the ring opening amidification reaction use a strong base catalyst, said catalyst is preferably the same and more preferably, it is sodium methoxide (MeONa).

[0056] In this embodiment, the obtained N,N-dimethyl hydroxyamide intermediate is preferably not isolated prior to its transesterification. Indeed after this first step, the unconverted DMA and the optional solvent can be removed through vacuum distillation for recycling and the carboxylic or carbonic acid ester derivative of formula R-(C=O)OR’ ’ (II) can be directly added to the crude residue.

[0057] Preferably, this reactant (II) is added in an amount of at least one equivalent with respect to N,N-dimethyl hydroxy amide intermediate.

[0058] In this embodiment, the strong base catalyst which has been added during the ring opening amidification step is usually enough to catalyze the transesterification reaction step but if necessary, an additional amount of a base catalyst, which can be different from the strong base catalyst used in the amidification step can also be added.

[0059] DMA: lactone molar ratios can range from stoichiometric ratio (1:1) to 3:1 (DMA excess) and stoichiometric ratios are usually preferred. The ring opening 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 -10°C to 90°C, preferably between 0°C and 80°C. The amount of catalyst used for this reaction is preferably comprised between 0.5 to 20 mol% with respect to the lactone and more preferably between 1 to 15 mol%.

[0060] In a further embodiment, the present invention also concerns a polar aprotic solvent obtainable by a process according as described above, said solvent having the generic formula (I) also described above.

[0061] In a preferred embodiment, R is selected from methoxy, phenyl or 3-oxobutyl (CH3-(C=O)-CH2-CH2-), preferably 3-oxobutyl.

[0062] In a further preferred embodiment, R’ is pentane-l,5-diyl.

[0063] In another preferred embodiment, R’ is propane- 1,3 -diyl.In a particularly preferred embodiment, R is 3-oxobutyl and R’ is pentane-1,5-diyl.

[0064] In another particularly preferred embodiment, R is 3-oxobutyl and R’ is propane- 1,3 -diyl.

[0065] In still a further embodiment, the invention concerns the use of the above polar aprotic solvent as solvent in agriculture formulations.

[0066] The inventive use of the polar aprotic solvent of the invention also includes the use as a co-solvent and / or as a crystallization inhibitor. The use as a cosolvent implies that the polar aprotic solvent is used in combination with at least one further solvent. The polar aprotic solvent 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.

[0067] The polar aprotic solvent 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.

[0068] The polar aprotic solvent 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.

[0069] In a further aspect, the present invention relates to an agriculture formulation (or agrochemical formulation) comprising an agricultural active compound and the polar aprotic solvent of the invention, wherein agriculture active compounds as described above can be used.

[0070] 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);

[0071] b) the polar aprotic solvent used as a solvent or co-solvent;

[0072] c) optionally at least one emulsifier or / and one surfactant; and

[0073] d) optionally water.

[0074] 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.

[0075] The agricultural active compounds are generally products in pure or highly concentrated form.

[0076] 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.

[0077] 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.

[0078] Non-limiting examples of fungicides suitable for use in the present invention include azoles such as e.g. prothioconazole, epoxi conazole, difenoconazole, propiconazole, cyproconazole, 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.

[0079] Particularly good results are obtained with azoxystrobin, difenoconazole and trifloxystrobin (see the examples).

[0080] The agricultural active compounds can be water-insoluble, at 20°C and at atmospheric pressure (i.e., 1.013xl05Pa).

[0081] 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).

[0082] 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.

[0083] 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 N-(n-butyl)thiophosphoric acid triamide (NBPT) and / or dicyandiamide (DCD).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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] Generally, the polar aprotic solvent 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.

[0089] It is possible to combine several agricultural active compounds in the agriculture formulation of the invention.

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

[0091] The term “biostimulant” 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.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.

[0092] 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 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-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 (IBA), 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-benzoyl adenine, 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.

[0095] The agriculture 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 (overtime and / or in temperature) of the emulsion, for example by avoiding separation of the phases.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.

[0097] Generally, the agrochemical formulation according to the invention further comprises at least one surfactant.

[0098] Advantageously, the surfactants that may be used in the invention are chosen from anionic, non-ionic, cationic, amphoteric or zwitterionic surfactants, and mixtures thereof.

[0099] Preferentially, the surfactants are chosen from anionic surfactants, nonionic surfactants, and mixtures thereof.

[0100] More preferentially, the surfactants are chosen from anionic surfactants, polyalkoxylated non-ionic surfactants, and mixtures thereof.

[0101] The emulsifiers and surfactants that may be used are different from the agricultural active compound(s).

[0102] By way of examples of anionic surfactants, mention may be made without any intended limitation thereto, of:

[0103] - 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,

[0104] - 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,

[0105] - 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 (ethoxylatedand / or propoxy lated) 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) Cs-Cso, preferably C10-C22 alcohol; of phosphoric acid and of a non-alkoxy lated C8-C2, preferably C10-C22 alcohol,

[0106] - 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.

[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.

[0108] By way of examples of non-ionic surfactants, mention may be made without any intended limitation thereto, of:

[0109] - 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 tristyrylphenols, 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 oxy ethylene units ; phosphated ethoxylated tri-(phenyl-l -ethyl) phenol containing 16 oxy ethylene units.

[0110] - 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.

[0111] - 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.

[0112] - 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.

[0113] Useful emulsifiers are in particular the following products, all marketed by the Applicant:

[0114] - Soprophor® TSP / 724: a surfactant based on ethopropoxylated tristyrylphenol,

[0115] - Soprophor® 796 / P: a surfactant based on ethopropoxylated tristyrylphenol,

[0116] - Soprophor® CY 8: a surfactant based on ethoxylated tristyrylphenol, - Soprophor® BSU: a surfactant based on ethoxylated tristyrylphenol, - Soprophor® S / 25: a surfactant based on ethoxylated tristyrylphenol, - Soprophor® 3D33: a surfactant based on ethoxylated tristyrylphenol, phosphate ester,

[0117] - Alkamuls® RC: a surfactant based on ethoxylated castor oil,

[0118] - Alkamuls® OR / 36: a surfactant based on ethoxylated castor oil,- Alkamuls® V02003: a surfactant based on ethoxylated castor oil, - Alkamuls® OL40: a surfactant based on ethoxylated sorbitan hexaoleate, - Alkamuls® T / 20: a surfactant based on ethoxylated sorbitan ester.

[0119] - Geronol® TBE724: a surfactant based on ethopropoxy lated tristyrylphenol,

[0120] - Geronol® TEB25: a mixture of surfactants based on ethoxylated castor oil, calcium dodecyl benzene sulfonate and alkoxylated polymers,

[0121] - Rhodacal® 60 / B: a surfactant based on dodecylbenzene sulphonate, - Rhodacal® 60 / BE: a surfactant based on dodecylbenzene sulphonate. 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.

[0122] 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.

[0123] 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.

[0124] The agriculture formulation according to the invention may further comprise at least one co-solvent, different from the polar aprotic solvent of the invention.

[0125] This other solvent or co-solvent can generally be selected from:

[0126] - linear or branched, saturated or unsaturated, aliphatic hydrocarbons, possibly containing a halogen -, phosphorus -, sulfur - and / or nitrogen atom and / or a functional group,

[0127] - carbocyclic or heterocyclic hydrocarbons, whether saturated, unsaturated or aromatic, possibly containing a halogen -, phosphorus -, sulfur - and / or nitrogen atom and / or a functional group,

[0128] More particularly, this co-solvent is chosen from:- 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;

[0129] - 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;

[0130] - alkyl mono-, di-, or tri-phosphates such as for example triethyl phosphate; tributyl phosphate; or tri-2-ethylhexylphosphate;

[0131] - aliphatic, cycloaliphatic or aromatic ketones such as for example dialkyl ketones; benzyl ketones; fenchone; acetophenone; cyclohexanone; alkyl cyclohexanones; isophorone; cyclopentanone.

[0132] - aliphatic, cycloaliphatic or aromatic alcohols such as for example glycols; 2-ethylhexanol; cyclohexanol; benzyl alcohols; tetrahydrofurfuryl alcohol;

[0133] - 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;

[0134] - fatty acids such as for example linoleic acid, linolenic acid, oleic acid; - carbonates such as for example propylene or butylene carbonate;

[0135] - amides such as for example dimethyl alkylamides, dimethyl-decanoamide; N-alkyl-pyrrolidones; dimethyl lactamide.

[0136] - alkyl ureas;

[0137] - amines such as for example alkanolamines, morpholine ;

[0138] - tetramethyl sulfone; sulfolane;

[0139] - dimethyl sulfoxide;

[0140] - halogenoalkanes or halogenated aromatic solvents such as for example chloroalkanes or chlorobenzene.

[0141] 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 madeof the product Alkamuls® OL700 marketed by the Applicant, alkanolamides, polymers.

[0142] 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.

[0143] 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.

[0144] 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 spray able diluted.

[0145] 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.

[0146] 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).

[0147] 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).

[0148] 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.

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

[0150] 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).

[0151] According to one embodiment of the invention, the agrochemical formulation according to the invention is aqueous.

[0152] 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.

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

[0154] According to a particular embodiment of the invention, the agriculture formulation may advantageously comprise:

[0155] 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,

[0156] 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,

[0157] 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,

[0158] 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,

[0159] 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.

[0160] Known conventional methods for preparing agriculture formulations may be implemented. It is possible to undertake this by simply mixing the constituents.

[0161] 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.

[0162] 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.Besides their use as solvents, co-solvents and / or crystallization inhibitors, particularly in agriculture formulations, the polar aprotic solvents of the invention are also useful as solvent for coating applications, the manufacturing of membranes, or solid batteries.

[0163] The polar aprotic solvents 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.

[0164] The polar aprotic solvents 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 poly condensates such as aromatic polyamides (aramids).

[0165] Moreover, the polar aprotic solvents of the invention can be used as cleaning solvent for the cleaning of equipment like reactors for instance, in particular polymerization reactors.

[0166] Since the polar aprotic solvents 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.

[0167] 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.

[0168] Examples

[0169] Example 1. Synthesis of the non-isolated intermediate N,N-dimethyl 6-hydroxycaproamide.

[0170] The reaction was conducted under an inert atmosphere and in a IL double jacketed reactor equipped with a mechanical stirrer (comprising a 4 inclined paddles stirring device) and baffles, a temperature probe, and a condenser set upat 20°C equipped with a temperature probe as well and connected to a receiving flask. A storage container filled with 104.81 g of caprolactone (0.918 mole) was connected to the reactor through a liquid addition pump.

[0171] In the reactor were added at room temperature:

[0172] - 330 mL of a commercial solution of DMA in ethanol (33 wt% concentration, 250.84 g of the solution, 82.78 g of DMA, 1.836 moles, 2 eq. wrt caprolactone).

[0173] - 4.78 g of sodium methylate (88 mmoles, -10 mol% wrt caprolactone). The obtained suspension was then allowed to stir (400 rpm) at 65-70°C and the caprolactone was progressively added into the reaction vessel with a flow rate of ~0.3 mL / min corresponding to a total feeding time of 6h00. The reaction progress was followed-up thanks toJH NMR spectroscopy and analysis after 8h00 total reaction time at 65-70°C indicated complete conversion of caprolactone with a selectivity of -93 mol% toward the desired adduct and only 3 mol% toward ethyl 6-hydroxy caproate by-product. The unconverted DMA and ethanol solvent were then removed through vacuum distillation (350 mbar, T°C in the reaction mass: 65°C, T°C recorded at the column head: 50°C) and the obtained crude residue was directly used as such for the next step in the same equipment.

[0174] Results of theJH NMR spectroscopy and analysis:

[0175] 'H NMR (CD3OD, 400 MHz) 6 (ppm): 3.57 (t, 2H, J = 6.5 Hz), 3.08 (s, 3H), 2.94 (s, 3H), 2.41 (t, 2H, J = 7.6 Hz), 1.72-1.52 (m, 4H), 1.48-1.36 (m, 2H).

[0176] Example 2. Synthesis of compound (I) with R = OMe (X’ = R” = CH3) and R’ = -CH2-CH2-CH2-CH2-CH2-.

[0177] 10 equivalents of dimethyl carbonate (488g, 5.309 moles) were added to a crude residue obtained according to the protocol of example 1 at room temperature (crude obtained from 75 g of starting caprolactone (0.637 mole) with an estimated yield of 83 mol% corresponding to - 0.529 mole of N,N-dimethyl 6-hydroxy caproamide).

[0178] The mixture was then allowed to stir [400 rpm] at 85-90°C and the reaction progress was followed up thanks to 'H NMR spectroscopy. Themethanol by-product formed during the reaction as well as some dimethyl carbonate were distilled out during the course of the reaction (28.78 g of recovered distillate). 'H NMR analysis after 2h00 reaction time at 85-90°C showed complete conversion of the intermediate toward the desired carbonate ester.

[0179] Then an aqueous H3PO4 solution (84 wt%, 2.38 g) was added into the reaction mass at room temperature for catalyst neutralization in order to reach 6.5 < pH < 7.5 (after IhOO stirring at 25°C, measured at 10 vol% dilution 25°C). The volatiles (DMC in excess, water, and MeOH) were removed through vacuum distillation (140 mbar, T°C in the boiler: 41 °C, T°C in the column head: 35°C).

[0180] The crude residue was re-solubilized in DMC (56 g) and the suspension was filtered in order to remove the phosphate salts.

[0181] The DMC solvent was evaporated and the crude was solubilized again in ethyl acetate. The organic phase was washed several times with saturated NaCl aqueous solution and the solvent was evaporated in order to recover 82.10 g of product as a yellow liquid. 'H NMR analysis indicated a purity of ~90 wt%.

[0182] Results of the 'H NMR spectroscopy and analysis:

[0183] 'H NMR (CD3OD, 400 MHz) 6 (ppm): 4.12 (t, 2H, J = 6.6 Hz), 3.74 (s, 3H), 3.06 (s, 3H), 2.93 (s, 3H), 2.39 (t, 2H, J = 7.6 Hz), 1.72-1.56 (m, 4H), 1.48-1.36 (m, 2H).

[0184] 13C NMR (CD3OD, 101 MHz) 6 (ppm): 175.5, 157.5, 69.1, 55.3, 37.9, 35.9, 34.0, 29.7, 26.7, 25.9.

[0185] Moisture content: 0.26% (Karl-Fischer).

[0186] Comparative Example 3. Synthesis of compound (I) with R = Phenyl and R’ = -CH2-CH2-CH2-CH2-CH2-.

[0187] Methyl benzoate (482.5 mL, 525.9 g, 3.824 moles, 4.6 eq.) was added at room temperature to a crude mixture obtained according to the protocol of example 1 (crude obtained starting from 104.81 g of caprolactone (0.918 mole) with an estimated yield of 91% corresponding to ~ 0.835 mole of N,N-dimethyl 6-hydroxy caproamide).The mixture was then allowed to stir at 85-90°C (400 rpm) and the methanol by-product formed during the reaction was distilled out in order to drive the reaction toward completion. In order to assist methanol removal, the reaction vessel pressure was decreased down to 550 mbar. The reaction progress was followed up thanks toJH NMR spectroscopy (with careful aliquot neutralization with acetic acid in order to avoid base catalyzed transesterification occurring in the NMR tube when CD3OD is used as the deuterated solvent).

[0188] After 5h30 reaction time at 85-90°C, the esterification conversion rate reached ~ 80 mol%. The temperature was then decreased down to 25°C and the mixture was neutralized with the addition of 3.3 g of aqueous H3PO4 (84% solution) in order to reach 6.5 < pH < 7.5 (after IhOO stirring at 25°C, measured at 10 vol% dilution 25°C).

[0189] The organic phase was then washed three times with a saturated NaCl solution followed by one time with an aqueous NaHCCfi 0.5 M solution and finally one time with an aqueous HC1 solution (0.1 M).

[0190] After phase separation, the excess of methyl benzoate, methanol, and water were then distilled out through vacuum distillation (10 mbar, T°C in the boiler: 92°C, T°C in the column head: 85°C), total mass recovered in the distillate: 464.95 g.

[0191] Finally, the obtained residue was redissolved in ethyl acetate and the solution was passed through a silica plug for discoloration. After ethyl acetate evaporation, around 112 g of an orange liquid was obtained with a1H NMR purity of around 80 wt%. The impurities were mainly 6-((6-(dimethylamino)-6-oxohexyl)oxy)-6-oxohexyl benzoate (~ 11 wt%) and 6-methoxy-6-oxohexyl benzoate (~ 7 wt%).

[0192] Results of the 'H NMR spectroscopy and analysis:

[0193] 'H NMR (CD3OD, 400 MHz) 6 (ppm): 8.00 (dd, 2H, J = 8.4 Hz, J = 1.3 Hz), 7.59 (t, 1H, J = 7.6 Hz), 7.46 (t, 2H, J = 7.6 Hz), 4.31 (t, 2H, J = 6.5 Hz), 3.03 (s, 3H), 2.90 (s, 3H), 2.38 (t, 2H, J = 7.6 Hz), 1.79 (quintet, 2H, J = 7.5 Hz), 1.67 (quintet, 2H, J = 7.5 Hz), 1.49 (quintet, 2H, J = 7.5 Hz).13C NMR (CD3OD, 101 MHz) 6 (ppm): 175.52, 168.09, 134.28, 131.73, 130.57, 129.69, 66.10, 37.92, 35.86, 34.05, 29.75, 27.01, 26.04.

[0194] Moisture content: 0.06% (Karl-Fischer).

[0195] Example 4. Synthesis of compound (I) with R = CH3-(C=O)-CH2-CH2- and R’ = -CH2-CH2-CH2-CH2-CH2-.

[0196] Methyl levulinate (308.9 g, 2.37 moles, 3.1 eq.) was added at room temperature to the crude mixture obtained according to the protocol of example 1 (crude obtained starting from 101 g of caprolactone (0.885 mole) with an estimated yield of 87% corresponding to ~ 0.770 mole of N,N-dimethyl 6-hydroxy caproamide).

[0197] The mixture was allowed to stir (500 rpm) at 85-90°C and 100-150 mbar pressure in order to distill out the methanol which was formed as a by-product during the reaction. The reaction progress was followed-up thanks to1H NMR spectroscopy (with careful aliquot neutralization with acetic acid in order to avoid base catalyzed trans-esterification occurring in the NMR tube when CD3OD is employed as deuterated solvent).

[0198] After 2h00 reaction, NMR analysis showed that the reaction conversion reached a plateau which was explained by the consumption of NaOMe catalyst under the reaction conditions. In order to improve the conversion rate, an additional quantity of l,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) (25.89 g, 170 mmoles, ~ 22 mol%) was added into the reaction mixture which was allowed to stir at 110-115°C, 50 mbar.

[0199] After an additional 5h00 reaction time, the esterification conversion rate reached 75 mol% and the reaction mass was allowed to cool down at room temperature.

[0200] The mixture was then neutralized with the addition of 10.5 g of an aqueous H3PO4 solution (85% solution) in order to reach 6.5 < pH < 7.5 (after IhOO stirring at 25°C, measured at 10 vol% dilution 25°C).

[0201] Ethyl acetate (200 mL) was added into the crude mixture and the organic phase was washed three times with a saturated aqueous solution of NaClfollowed by one washing with an aqueous solution of NaHCCh (0.5 M) and a final washing with saturated aq. NaCl.

[0202] Ethyl acetate and unconverted methyl levulinate were then removed through vacuum distillation (T°C in the boiler going from 100°C to 150°C and pressure dropping from 200 mbar to 5 mbar) allowing to recover approximately 79 g of methyl levulinate.

[0203] The obtained crude material (124 g) was then purified through distillation on a wiped film evaporator (190°C, 1.2 mbar) allowing to recover the purified product as a yellow liquid (79.2 g).

[0204] Results of the 1H NMR spectroscopy and analysis:

[0205] 'H NMR (CD3OD, 400 MHz) 6 (ppm): 4.07 (t, 2H, J = 6.6 Hz), 3.07 (s, 3H), 2.93 (s, 3H), 2.78 (t, 2H, J = 6.6 Hz), 2.53 (t, 2H, J = 6.4 Hz), 2.39 (t, 2H, J = 7.7 Hz), 2.17 (s, 3H), 1.70-1.58 (m, 4H), 1.49-1.36 (m, 2H).

[0206] 13C NMR (CD3OD, 101 MHz) 6 (ppm): 209.24, 175.46, 174.50, 65.57, 38.75, 37.94, 35.85, 34.02, 29.85, 29.62, 29.03, 26.84, 25.99.

[0207] Moisture content: 0.05% (Karl-Fischer).

[0208] Example 5. Synthesis of the non isolated intermediate N,N-dimethyl 4-hydroxybutanamide.

[0209] The reaction was conducted under an inert atmosphere and in a IL double jacketed reactor equipped with a mechanical stirrer (comprising a 4 inclined paddles stirring device) and baffles, a temperature probe, and a condenser set up at 0°C equipped with a temperature probe as well and connected to a receiving flask. A syringe filled with 85.99 g of gamma-butyrolactone (1 mole) was connected to the reactor through a Teflon pipe.

[0210] In the reactor were added at room temperature:

[0211] - 354.81 mL of a commercial solution of DMA in ethanol (33 wt% concentration, 269.66 g of the solution, 88.99 g of DMA, 1.99 moles, 2 eq. wrt gamma-buty r ol acton e) .

[0212] - 5.40 g of sodium methylate (99.9 mmoles, ~10 mol% wrt gammabutyrolactone).The obtained suspension was then allowed to stir (500 rpm) at 65-75°C and the gamma-butyrolactone was progressively added into the reaction vessel over 6h00 corresponding to a feeding rate of 0.20-0.25 mL / minute. The reaction progress was followed-up thanks toJH NMR spectroscopy and analysis after 7h00 total reaction time at 65-75°C indicated complete conversion of gammabutyrolactone with the formation of the desired N,N-dimethyl 4-hydroxybutanamide. The unconverted DMA and ethanol solvent were then removed through vacuum distillation (200 mbar, T°C in the reaction mass: 60°C, T°C recorded at the column head: 50°C) and the obtained crude residue was directly used as such for the next step in the same equipment.

[0213] Results of theJH NMR spectroscopy and analysis:

[0214] 'H NMR (CDCh, 400 MHz) 6 (ppm): 3.44 (t, 2H, J = 5.7 Hz), 2.85 (s, 3H), 2.74 (s, 3H), 2.28 (t, 2H, J = 7.0 Hz), 1.67 (quin, 2H, J = 6.4 Hz).

[0215] Example 6. Synthesis of compound (I) with R = CH3-(C=O)-CH2-CH2- and and R’ = -CH2-CH2-CH2-.

[0216] Ethyl levulinate (432.01 g, 2.996 moles, 3 eq.) was added at room temperature to the crude mixture obtained according to the protocol of example 5.

[0217] The mixture was allowed to stir (500 rpm) at 120-130°C and 450-500 mbar pressure in order to distill out the ethanol which was formed as a byproduct during the reaction. The reaction progress was followed-up thanks to1H NMR spectroscopy (with careful aliquot neutralization with acetic acid in order to avoid base catalyzed trans-esterifi cation occurring in the NMR tube when CD3OD is employed as deuterated solvent).

[0218] After 2h00 reaction, NMR analysis showed that the reaction conversion reached a plateau which was explained by the consumption of NaOMe catalyst under the reaction conditions. In order to improve the conversion rate, an additional quantity of l,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) (15.2 g, 99.88 mmoles, ~ 10 mol%) was added into the reaction mixture which was allowed to stir at 130°C, 450 mbar.After an additional 4h00 reaction time, the esterification conversion rate reached approximately 75 mol% and the reaction mass was allowed to cool down at room temperature.

[0219] The mixture was then neutralized with the addition of 20.3 g of an aqueous H3PO4 solution (85% solution) in order to reach pH~6.3 (after 0h30 stirring at 25°C, measured directly in the mixture at 25°C).

[0220] Ethyl acetate (200 mL) was then added into the crude mixture and the organic phase was washed with a saturated aqueous solution of NaHCCh followed by two washes with a saturated aqueous solution of NaCl.

[0221] Ethyl acetate and unconverted ethyl levulinate were then removed through vacuum distillation (T°C in the boiler going from 100°C to 150°C and pressure dropping from 400 mbar to 6 mbar) allowing to recover approximately 291.9 g of ethyl levulinate.

[0222] Residual traces of ethyl levulinate in the crude material were then removed through vacuum distillation conducted at 180°C, 5 mbar during 3h00 allowing to recover at the end 108.6 g of crude material as a black oil.

[0223] The obtained crude material was then purified through distillation on a wiped film evaporator (193°C, 1.2 mbar) allowing to recover the purified product as an orange liquid (59 g).

[0224] Results of theJH NMR spectroscopy and analysis:

[0225] 'H NMR (CDCI3, 400 MHz) 6 (ppm): 4.03 (t, 2H, J = 6.2 Hz), 2.92 (s, 3H), 2.85 (s, 3H), 2.66 (t, 2H, J = 6.4 Hz), 2.46 (t, 2H, J = 6.4 Hz), 2.29 (t, 2H, J = 7.4 Hz), 2.09 (s, 3H), 1.87 (quin, 2H, J = 6.9 Hz).

[0226] 13C NMR (CDCI3, 101 MHz) 6 (ppm): 206.76, 172.72, 172.06, 64.11, 37.92, 37.20, 35.45, 29.89, 29.47, 27.94, 24.25.

[0227] Example 7. Solubilization of agriculture active ingredients.

[0228] Solubility tests were carried out consisting of assessing the solubility of some key strategic fungicides in the solvents of the present invention at different concentrations and at 25°C.

[0229] The solutions were monitored for 1 week to watch for any active ingredient crystallization over aging.Mixtures were prepared by solubilizing an active ingredient at a certain concentration (g / 1) in solvent systems (pure). Each active was individually weighed and added to the solvent system.

[0230] The mixture was stirred at 60 rpm using a rotator drive for 24h at room temperature and for 48h00 at room temperature for the high loadings due to viscosity build-up.

[0231] The solubilizing capabilities of each system were evaluated based on visual observations at room temperature (1 week). At a given concentration, if the mixture was limpid (homogeneous liquid phase), the active ingredient was considered to be soluble in a solvent at this concentration. However, if a turbid solution, crystal, suspended particles, or deposit appeared, the active ingredient was not soluble anymore in a solvent and the maximal solubility was reached.

[0232] The maximal solubility was defined as the maximum amount of active ingredient(s) that could be dissolved in the solvent system, equal to the amount at which the mixture remained limpid. The solubility results obtained at 25°C for a set of active ingredients in the solvents of the present invention were indicated in the table below and were compared with the benchmark (Rhodiasolv® PolarClean for the compound obtained in example 2 and ADMA-10 for the compounds obtained in examples 3 and 4).

[0233] In this table, the first column indicates the solvent used and:

[0234] - P stands for Prothioconazole

[0235] - Te stands for Tebuconazole

[0236] - A stands for Azoxy strobin

[0237] - S stands for Saflufenacil

[0238] - D stands for Difenoconazole

[0239] - F stands for Fluxapyroxad

[0240] - Tr stands for Trifl oxy strobin

[0241]

[0242]

[0243] As can be seen in the table above, the compound obtained according to comparative example 3 is less performing as solvent than the compounds obtained in the examples according to the invention. In addition, the compound of comparative example 3 was found to be unstable at low temperatures (0°C or lower).

[0244] The compounds obtained according to examples 4 and 6 are globally better than ADMA-10: indeed, whereas they are slightly less efficient in solubilizing prothioconazole and tebuconazole, they are however, better for the solubilization of azoxystrobin, fluxapyroxad, and trifloxystrobin.

[0245] In addition, the compounds of the present invention displayed an excellent biodegradability profile; for example, the compound obtained according to example 4 reached more than 75% of biodegradation rate after 12 days in a readily biodegradability assay performed according to the OECD301F guidelines.

Claims

1. C L AI M S1. A process for the synthesis of a polar aprotic solvent, wherein said polar aprotic solvent is obtained through a transesterification reaction of aN,N-dimethyl hydroxyamide intermediate with a carboxylic or carbonic acid ester derivative of formula R-(C=O)OR” (II) where R” is an alkyl group containing between 1 and 6 carbon atoms and where R is an alkoxy group of formula (-OX’) where X’ is an alkyl group having between 1 and 6 carbon atoms or an oxoalkyl group having between 3 to 6 carbon atoms.

2. The process according to claim 1, wherein in the transesterification reaction, the N,N-dimethyl hydroxyamide intermediate is reacted with a dialkyl carbonate or an alkyl levulinate, preferably an alkyl levulinate.

3. The process according to claim 1 or 2, wherein the alkyl levulinate is methyl levulinate or ethyl levulinate.

4. The process according to any of the preceding claims, wherein the transesterification reaction is conducted in a basic medium, using a base catalyst.

5. The process according to any of the preceding claims, wherein the N,N-dimethyl hydroxyamide intermediate is obtained through a ring opening amidification of a lactone with dimethylamine.

6. The process according to any of the preceding claims, wherein the lactone is selected from gamma-lactones, delta-lactones and epsilon-lactones.

7. The process according to claim 6, wherein the lactone is selected from gamma-butyrolactone, delta-valerolactone and epsilon- caprolactone.

8. The process according to claim 7, wherein the lactone is epsilon-caprolactone or gamma-butyrolactone.

9. The process according to any of claims 5 to 8, wherein the ring opening amidification of the lactone is catalyzed by a strong base and is preferably conducted in the presence of a solvent, more preferably an alcohol.

10. The process according to claim 9, wherein both the transesterification reaction and the ring opening amidification reaction use a strong base catalyst, andwherein said strong base catalyst is the same, and preferably is sodium methoxide (MeONa).

11. A polar aprotic solvent obtainable by a process according to any of the preceding claims, said solvent having the generic formula (I),whereinR is an alkoxy group of formula (-OX’) where X’ is an alkyl group having between 1 and 6 carbon atoms or R is an oxoalkyl group having between 3 and 6 carbon atoms; andR’ is an alkanediyl group selected from propane-1, 3-diyl eventually substituted by one or more C1-C3 alkyl groups, butane- 1,4-diyl eventually substituted by one or more C1-C3 alkyl groups, and pentane- 1,5 -diyl eventually substituted by one or more C1-C3 alkyl groups.

12. The polar aprotic solvent according to claim 11, wherein R is selected from methoxy or 3-oxobutyl (CH3-(C=O)-CH2-CH2-), preferably 3-oxobutyl.

13. The polar aprotic solvent according to claim 12, wherein R is 3-oxobutyl and R’ is pentane-l,5-diyl.

14. Use of polar aprotic solvent according to any of claims 11 to 13, or obtained by a process according to any of claims 1 to 10, as solvent in agriculture formulations.

15. Polar aprotic solvent according to any of claims 11 to 13, or obtained by a process according to any of claims 1 to 10, which is biodegradable, nontoxic, safe to the environment and based on renewable raw materials, and is preferably obtained through the transesterification of a N,N-dimethyl hydroxyamide intermediate with bio-based methyl or ethyl levulinate.

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