WO2025224140A1 - Use of 2-piperidinone derivatives as solvents - Google Patents

Abstract

The use of N-alkyl 2-piperidinone 5-carboxylic acid esters as solvent, e.g. for the solubilization of agricultural active agents in agriculture formulations.

Description

USE OF 2-PIPERIDINONE DERIVATIVES AS SOLVENTS

This application claims priority to the application filed on April 24, 2024 in Europe with Nr 24315218.8, the whole content of this application being incorporated herein by reference for all purposes.

TECHNICAL FIELD

The present invention relates to the use of 2-piperidinone derivatives (esters) as solvents, more particularly as a polar aprotic solvents e.g. for the solubilization of agricultural active agents in agriculture formulations.

TECHNICAL BACKGROUND

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.

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.

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.

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.

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.

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.

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.

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.

WO2012034689 relates to the use of 2-pyrrolidinone derivatives as solvents for agriculture formulations. However, the compounds described in WO2012034689 display several drawbacks:

- They are obtained from itaconic acid which, while being bio-based, is not a widely available raw material therefore likely to pose significant sourcing issues. Acrylate esters which can be used as raw materials according to one aspect of the present invention, on the contrary, really are commodity raw materials. Moreover, acrylate esters could be bio-based as well if produced for example from bio-based acrylic acid obtained through catalytic dehydration of lactic acid (see for example patent US 9.926.256).

- Their generic structure features a 2-pyrrolidinone skeleton from which several solvent derivatives are known to possess reprotoxicity (for example NMP, NEP, and even the parent compound 2-pyrrolidone. . .). On the contrary the 2-piperidinone derivatives of the present invention are not known to possess any reprotoxicity issues. Their chemical structure is quite close to a metabolite commonly found in the human body (coming from NAD degradation or following caffeine or niacin consumption: N-methyl-2-pyridone-5-carboxamide, commonly called “2PY) making unlikely that toxicity concerns exist for the compounds of the present invention.

- In addition, QSAR in-silico predictions (using the OECD Toolbox software) have been performed to compare the pyrrolidinone derivative of Example 1 of WO2012034689 which has a similar substituent pattern than the compound IVa of the present invention. While a skin sensitizing alert has been found for the pyrrolidinone derivative, compound (IVa) was found negative for skin sensitization showing that the compounds of the present invention seem to have a global better toxicity profile than the pyrrolidinone derivatives of WO2012034689. - Finally, the molecules exemplified in WO2012034689 were all used in replacement of NMP in different EC (Emulsifiable Concentrates) formulations, meaning they are water miscible and hence, need to be mixed with non water miscible co-solvents in order to keep the active ingredients in the organic (solvent) phase and prevent them from crystallizing into the aqueous phase when used in diluted version in water.

- And last but not least: the pyrrolidinone derivative of Example 1 of WO2012034689 has a melting point of +15°C, meaning that problems may arise depending on its handling and use conditions in agricultural formulations, especially in dispersible concentrates (DC) formulations. In contrast, the compound (IVa) according to the present invention and having the same substituents pattern than the pyrrolidinone derivative of example 1 of WO2012034689 does not have any fusion temperature up to -150°C but merely a glass transition temperature at about -74°C (measured in the form of a mixture of (IVa) : (IVb) = 80 : 20 wt% compounds according to the present invention). This comparison tends to suggest that the compounds of the present invention possess melting points significantly lower than the pyrrolidinone derivatives of WO2012034689 which is an important technical advantage for solvents.

It is accordingly the object of the present invention to provide a polar aprotic solvent that can potentially be bio-sourced or upcycled, whose raw material is a commodity and which shows improved solubilization efficiency for a wide range of agricultural active compounds, while not posing any (repro)toxicity issues.

It is also an object of the present invention to provide polar aprotic solvents which have none or a very low melting point and hence particularly suitable for use in DC formulations.

It is also an object of the present invention to provide polar aprotic solvents which are not water miscible and hence particularly suitable for use in EC formulations.

SUMMARY OF THE INVENTION

In a first aspect, the present invention concerns a process for the manufacture of N-alkyl 2-piperidinone 5-carboxylic acid esters of formula (IV): said process comprising the following steps:

1. head-to-tail catalytic dimerization of an acrylate ester of formula (I) to a methyleneglutarate bis-ester of formula (II):

2. tandem condensation/cyclization of the methyleneglutarate bis-ester

(II) with an alkyl amine of formula (III):

R1-NH2

(HI) wherein Ri and R2 are linear or branched or cyclic alkyl groups having from 1 to 12 C atoms.

This synthesis route is shown below:

In an embodiment of the present invention, the manufacturing process can comprise an additional step of catalytic transesterification of compound (IV) with an alcohol of formula FC’OH in order to generate a derivative of formula (IV) having the substituent R2’ instead of R2 (with coproduction of the alcohol R2OH) wherein R2’ is a linear or branched or cyclic alkyl group having from 1 to 12 C atoms different from R2. This additional step allows to easily modulate the nature of the group R2 in formula (IV). This additional step can be performed in a “one- pot” mode after the amine addition/cyclization step and removal of unreacted amine and dimer. Alternatively, it can be performed in a separate and distinct step after purification of compound (IV).

In further aspect, the present invention concerns the use of the esters of formula (IV) as solvent, e.g. for the solubilization of agricultural active agents in agriculture formulations.

In yet a further aspect, the present invention concerns specific esters of formula (IV).

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

DETAILED DESCRIPTION OF THE INVENTION

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

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’. 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.

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.

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

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”, 2^nd edition, William Andrew Publishing, 2015.

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 (1 -ami de-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).

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

The term “% w/v” refers to the weight amount of the respective ingredient based on a total volume of the formulation. The embodiments and preferred embodiments according to the invention are further defined hereinafter. The preferred embodiments are preferred alone or in combination. Further, it is to be understood that the following preferred embodiments refer to all aspects of the present invention, i.e. the compound, the method, the formulation as well as the use of the compound.

In one aspect, the present invention relates to a process for the manufacture of N-alkyl 2-piperidinone 5-carboxylic acid esters of formula (IV), as described above.

This manufacturing process displays several advantages:

1. Excellent atom economy with only the alcohol R2-OH being generated as the by-product during the second amidation step (and optionally during the last transesterification step if needed) but that can be easily valorized.

2. Energetically frugal process as all reaction steps can occur in relatively smooth conditions (reaction temperatures usually below 120-140°C).

3. When using non bulky amines, no catalyst is required for the second amidification step as the conjugate addition of the amine is straightforward and the cyclization driving force makes this transformation accessible without any strong base catalyst. In some cases however, a low and catalytic amount of a base is needed when using bulky amines R1-NH2. In that case the catalyst is easily neutralized at the end of the reaction before product distillation.

4. Can provide the final product in excellent purity and yields.

5. Starts from the widely available and cheap (and potentially biobased or up-cycled) acrylate esters as raw material.

6. This process is quite general allowing to tune the physical properties of the final product by modulating the Ri and R2 groups.

7. If starting from bio-based (or upcycled) acrylic acid can provide access to bio-based solvents.

Step 1. of the process of the invention, i .e. the head-to-tail catalytic dimerization of an acrylate ester of formula (I) to a methyleneglutarate bis-ester of formula (II), is preferably conducted as described in patent applications WO23066844 and WO23066829 in the name of the Applicant.

In a preferred embodiment, step 1. is conducted in the presence of a catalyst of formula (V) (V) wherein

R3 and R4 are identical or different, and are either aliphatic groups or form together with the N atom a heteroaliphatic cycle;

Ra is a hydrocarbyl group;

Rb is either an aliphatic group or NR5R6 with R5 and Re being identical or different, and being either aliphatic groups or forming together with the N atom a heteroaliphatic cycle.

Preferably, in the catalyst of formula (V), Ra is a phenyl, R3 and R4 are ethyl and Rb is NRsRe with R5 and Re being ethyl.

In a preferred embodiment, step 1. is conducted in the presence of a compound A being a tertiary alcohol or a silanol, preferably a tertiary alcohol, such as tert-butanol, tert-amyl alcohol or pinacol and more preferably tert- butanol. In this embodiment, the molar ratio [compound A]/[alkyl acrylate according to formula (I)] is typically selected from about 4: 1 to about 0.01 : 1, preferably from about 2: 1 to about 0.1 : 1 and more preferably from about 0.5: 1 to about 0.1 : 1.

In a preferred embodiment, step 1. is performed in an organic solvent, preferably an aprotic solvent, more preferably selected from tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), toluene, xylene, anisole, diethyl ether, tert-butyl methyl ether (MTBE), dichloromethane (DCM), chloroform, dioxane, pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, benzene and acetonitrile, still more preferably selected from MeTHF, anisole and toluene.

In still a further preferred embodiment (combinable with those described above, and which are all combinable by the way), step 1. is performed at a temperature ranging from about 20°C to about 120°C, preferably about 20°C to about 80°C, more preferably about 25°C to about 60°C.

Step 2 of the process of the invention, i.e. the tandem condensation/cyclization of the methyleneglutarate bis-ester (II) with an alkyl amine of formula (III), is preferably conducted in the absence of a solvent or alternately an additional solvent can be used during this step which will have to be later removed and recycled. A solvent can be useful for example when using volatile low molecular weight amines such as for example methylamine which is gaseous at room temperature. In that case commonly used solvents are alcohols, for example methanol or ethanol, as solution of amines in alcohol solvents are commercially available. In that case it is preferable to use as the solvent the alcohol R2OH derived from the bis-ester (II). When the alcohol solvent is different form the alcohol R2OH, transesterification can occur during this step as the result of the basic conditions resulting to a mixture of compounds (IV) having different R2 groups. Such mixture can be however useful as such.

This step is usually conducted without any catalyst and at a temperature ranging from room temperature to 150°C. Alternatively, basic compounds can be used as catalysts when employing bulky amines R1-NH2. As examples of suitable base catalysts one can mention NaOMe, KOMe, LiOMe, KOtBu, DBU (1,8- Diazabicyclo[5.4.0]undec-7-ene), or heterogeneous solid base catalysts such as K2CO3, MgO etc. . . When a homogeneous base catalyst is employed, it is neutralized by a suitable acid (e.g. H2SO4, KHSO4, methanesulfonic acid etc..) at the end of the reaction and before product distillation. When a heterogenous base catalyst is used, it is preferentially filtered out before the distillation. In terms of implementation, the dimer of formula (II) can optionally be progressively added to the amine. Alternatively, the amine reactant (III) can be progressively fed into the dimer of formula (II). As already mentioned, during this step there is also coproduction of an alcohol R2OH which can be separated through distillation and valorised if needed. The final product of formula (IV) can be easily isolated and purified thanks to vacuum distillation. In addition, unreacted amine of formula (III) and dimer of formula (II) can be recovered and recycled for the next batch allowing to increase the overall yield of the process.

As already mentioned above, it is possible to include an additional step of catalytic transesterification of compound (IV) with an alcohol of formula R2’0H in order to generate a derivative of formula (IV) having the substituent R2’ instead of R2 (with coproduction of the alcohol R2OH). This additional step allows to easily modulate the nature of the group R2 in formula (IV). This additional step can be performed in a “one-pot” mode after the amine addition/cyclization step and removal of unreacted amine and dimer. Alternatively it can be performed in a separate and distinct step after purification of compound (IV). This transesterification step can be conducted using preferably acid catalyst such as for example H2SO4, methanesulfonic acid, para- toluenesulfonic acid, triflic acid or heterogeneous solid catalysts such as amberlyst resins or zeolite catalysts. The catalyst is usually used at a loading ranging from 0.1 mol% to 20 mol% with respect to (IV). The new alcohol reagent RVOH can be used in excess, in a batch mode or in a fed-batch mode and the R2OH by-product can be progressively removed during the reaction through distillation in order to drive the equilibrium toward completion. This transesterification reaction is usually performed at a temperature ranging from 80°C to 200°C. The final product can be isolated and purified through distillation.

The present invention also concerns esters of formula (IV) obtainable by the above described process.

In a preferred embodiment of the invention, at least one of Ri and R2 is a methyl group.

In a first preferred sub-embodiment of the invention, Ri is methyl and R2 is a linear or branched or cyclic alkyl group having from 3 to 12 C atoms.

In a second preferred sub-embodiment of the invention, R2 is methyl and Ri is a linear or branched or cyclic alkyl group having from 5 to 12 C atoms.

The present invention also concerns the use of esters of formula (IV) as solvent, e.g. for the solubilization of agricultural active agents in agriculture formulations. In the following description, reference is made either to ester (singular) or esters (in plural), being understood that one ester of formula (IV) can be used as solvent, or a mixture involving at least 2 esters of formula (IV) can be used as solvent. Such mixtures are namely generated when an alcohol solvent, being different from the alcohol R2OH from which derives the acrylate ester (I), is used during step 2 of the process of the invention i.e. the tandem condensation/cyclization. This can be the case for instance when methylamine in an alcohol solvent is used as the amine in step 2 i.e. when Ri as defined above is methyl. Alternatively, a mixture of at least 2 esters of formula (IV) can be generated when a mixture of alcohols R2’0H is used during the optional transesterification step.

Hence, in one embodiment of the present invention, when Ri as defined above is methyl, then the solvent used according to the present invention may comprise at least 2 esters of formula (IV). In particular, the solvent may comprise at least esters of formula (IVa) and (IVb) as defined in Example 1 of the present specification, i.e. respectively a compound of formula (IV) with Ri = R2 = -CH3 (IVa) and a compound of formula (IV) with Ri = -CH3 and R2 = -Ethyl (IVb). The compounds of formula (IV) have shown excellent solvent properties of interest for the formulation of phytosanitary active ingredients. Indeed, we show that compounds of formula (IV) possessing Ri = R2 = -CH3 is a water miscible polar aprotic solvent displaying excellent solubilization performances on a wide range of active ingredients allowing to reach high active ingredient concentration solutions that are stable on ageing even at low temperature. Hence, in a first preferred embodiment, the present invention concerns the use of compounds of formula (IV) where both Ri and R2 are methyl groups, as solvents.

Even if a complete solubility performance comparison has not been made yet, in WO2012034689, the maximal solubility in the pyrrolidinone derivative possessing Ri = R2 = -CH3 (hence according to example 1 of this document) reached for tebuconazole at 25°C is 39.3 wt%. In our case the maximal solubility measured in (IV) for tebuconazole at 25°C is > 40 wt% (higher loadings were not investigated because of viscosity build-up) showing that the compounds of the present invention display higher intrinsic solubilization power.

The inventors also found out that by extending the Ri alkyl chain length it is possible to reduce the water miscibility of (IV) while keeping excellent solubilization performances. This is exemplified by (IV) possessing R2 = -CH3 and Ri = -nCeHn or the derivative (IV) with R2 = -CH3 and Ri = cHex (cyclohexyl). The corresponding non water miscible yet polar versions of (IV) are also of high interest for agriculture formulations due to their ability to form emulsion in the presence of a suitable emulsifier upon water addition making them also attractive solvent candidates for e.g. EC, EW or ME type formulations. This property should actually extend to Ri alkyl groups possessing up to 12 C atoms. Hence, in a second preferred embodiment, the present invention concerns the use of compounds of formula (IV) where R2 is a methyl groups and Ri is a linear or branched alkyl group having from 2 to 12 C atoms, as solvents.

In a preferred sub-embodiment, the present invention concerns the use of compounds of formula (IV) where R2 is methyl and Ri is a linear or branched or cyclic alkyl group having from 5 to 12 C atoms. This sub-embodiment has the advantage of covering molecules which have low water miscibility (typically < 5 wt%). This is an important technical advantage for emulsifiable concentrate formulations (EC) because using a non water miscible solvent allows for the formation of oil-in-water emulsions after water dilution during the use of the formulation and prevents the recrystallization of the active ingredient. If water- miscible solvents are used, it is therefore necessary to mix them with non-water miscible co-solvents to ultimately achieve a solvent mixture that is overall non- miscible with water which adds significant complexity in the formulation system. In this sub-embodiment, with a single solvent, it is possible to combine both good solubilization performance and non-miscibility with water. Preferably, Ri is a linear or branched or cyclic alkyl group having from 6 to 8 C atoms. Molecules where R2 is methyl and Ri is nHex (nHexyl) or cyclohexyl (cHexyl) were successfully synthesized and tested: see Examples 3, 5 and 6.

Alternatively, compounds of formula (IV) where Ri is a methyl group and R2 is a longer chain alkyl group might show similar properties that is to say low water miscibility and yet high polarity. Hence, in a third preferred embodiment, the present invention concerns the use of compounds of formula (IV) where Ri is a methyl groups and R2 is a linear or branched or cyclic alkyl group having from 2 to 12 C atoms, as solvents. These compounds generally have very low melting points, making them especially useful in DC formulations. It is namely so that such formulations generally only include, besides the active ingredient and the solvent, small amounts of other ingredients like surfactants or dispersing agents. And such compositions nevertheless should stay stable at -10°C without any precipitation/solidification, which makes the use of solvents according to this embodiment particularly interesting as they could be used as such without the need for additional polar solvents. On the other hand, the pyrrolidinone derivatives described in WO2012034689 possess high melting points (for example +15°C for the derivative with Ri = R2 = -CH3), therefor when used as the sole solvent in DC formulations, solvent solidification is likely to occur at low temperature, for example - 10°C requiring therefor to use additional low melting point co-solvents in order to maintain the formulation liquid at low temperature.

The inventive use of the esters 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 ester of formula (IV) is used in combination with at least one further solvent. The ester of formula (IV) 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.

The ester of formula (IV) 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 optionally bio-based. The ester of formula (IV) 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.

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

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) at least one ester of formula (IV) used as a solvent or co-solvent; c) optionally at least one emulsifier or/and one surfactant or/and dispersing agent; and d) optionally water.

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.

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

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.

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.

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.

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

The agricultural active compounds can be water-insoluble, at 20°C and at atmospheric pressure (i.e., 1.013xl0⁵ Pa).

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., 1.013xl0⁵ Pa).

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.

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.

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.

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

According to a particular embodiment of the invention (concentrated 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.

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.

Generally, the ester of formula (IV) 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.

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

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

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.

Generally, this is a substance or microorganism that, when applied to seeds, plants or on the rhizosphere, can stimulate natural processes to enhance or benefit nutrient uptake, nutrient use efficiency, tolerance to abiotic stress, or crop quality and yield.

Non-limiting examples of biostimulants include seaweed extracts (e.g., ascophyllum nodosum), humic acids (e.g., potassium humate), fulvic acids, myoinositol, glycine, and combinations thereof.

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

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 (BP A), N-(2-chloro- 4- pyridyl)-N-phenylurea, gibberellic acid (GA3), gibberellins, gibberellins A4 + A7 (GA n), ethylene and abscisic acid.

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

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.

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.

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

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

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

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

- 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,

- 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,

- 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,

- 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.

The anionic surfactants may be in the acid form (they are potentially anionic), or in a partly or totally salified form with one counter-ion. The counterion may be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or moreover even an ammonium ion of formula N(R)4⁺ in which the R groups, either identical or different, represent a hydrogen atom or a C1-C4 alkyl group optionally substituted with an oxygen atom.

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

- 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 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.

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

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

- sorbitan esters, optionally polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated), more particularly the cyclised sorbitol esters of CIO-C2O fatty acids such as lauric acid, stearic acid, or oleic acid, and comprising a total number of alkoxylated units comprised between 2 and 50.

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

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

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

- 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 tri styrylphenol,

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

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

- 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.

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

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

- 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. 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.

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.

The agriculture formulation according to the invention may further comprise at least one co-solvent, different from the ester of formula (IV).

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,

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

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;

- 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;

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

- aliphatic, cycloaliphatic or aromatic ketones such as for example dialkyl ketones; benzyl ketones; fenchone; acetophenone; cyclohexanone; alkyl cyclohexanones; isophorone; cyclopentanone. - aliphatic, cycloaliphatic or aromatic alcohols such as for example glycols; 2-ethylhexanol; cyclohexanol; benzyl alcohols; tetrahydrofurfuryl alcohol;

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

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

- carbonates such as for example propylene or butylene carbonate;

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

- alkyl ureas;

- amines such as for example alkanolamines, morpholine ;

- tetramethyl sulfone; sulfolane;

- dimethyl sulfoxide;

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

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.

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.

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.

Advantageously, the agriculture formulation according to the invention is in a liquid form, at 20°C and at atmospheric pressure (i.e., 1.013xl0⁵ Pa) and may be in the form of a concentrate of agricultural active compound(s), a diluted concentrate, or a sprayable diluted.

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.

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).

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).

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.

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

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).

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

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.

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.

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

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

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.

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 esters of formula (IV) are also useful as solvent for coating applications, the manufacturing of membranes, or solid batteries.

The ester of formula (IV) can furthermore be used in recycling processes of polymers, especially chemically resistant polymers like PVDF or PVDC (poly vinylidene chloride), still as a replacement of polar solvents such as NMP, DMF, DMSO, acetophenone and DMAc.

The ester of formula (IV) 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).

Moreover, the ester of formula (IV) can be used as cleaning solvent for the cleaning of equipment like reactors for instance, in particular polymerization reactors. Since the esters 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.

Examples

Example 1: Synthesis of a mixture of compounds (IV) with Ri = R2 = -CH3 (IVa) and of compounds (IV) with Ri = -CH3 and Rz = -Ethyl (IVb)

The precursor dimethyl 2-methyleneglutarate has been produced starting from methyl acrylate according to the protocol described in the patents WO23066844 & WO23066829.

See in particularly the examples K2 or K3 of the patent WO23066829 (page 25).

This reaction has been conducted under an inert argon atmosphere and in carefully dried vessel.

The tandem condensation/cyclization reaction has been conducted in a IL double jacketed reactor equipped with a mechanical stirrer (4 inclined plows stirrer devise with integrated baffles), a temperature probe, a condenser cooled at 7°C and a distillation apparatus connected to a 500 mL round bottom flask collector. The IL reactor was also connected to a pump through a Teflon pipe for the progressive addition of dimethyl 2-methyleneglutarate reactant.

In the reactor was loaded at room temperature 163.9 g of a methylamine in ethanol solution (33 wt% methylamine concentration, 216.8 mL, 1.742 moles of methylamine, 1 eq.).

In a feeding tank connected to the pump through a Teflon pipe was added at room temperature 300 g of dimethyl 2-methyleneglutarate (1.742 moles, 1 eq.).

The methylamine/ethanol solution in the IL reactor was cooled down at 5°C and stirred at 350 rpm; dimethyl 2-methyleneglutarate was progressively added into the reaction vessel over 40 minutes (corresponding to a flow of 7.5 g/minute). Upon addition a very slight exothermy was observed. At the end of the addition, the reaction mixture was allowed to stir at room temperature and the reaction progress is followed-up thanks to ¹ H NMR analysis.

After 50 minutes stirring at 25°C after the end of the addition, the conversion level of dimethyl 2-methyleneglutarate was about 47%. In order to speed up the reaction kinetic, the temperature of the reaction mass was allowed to increase to 50°C and the mixture was stirred during additional 7 hours at 50°C allowing to reach a conversion level around 85 mol%.

The crude mixture was then distilled under vacuum in order to collect 5 main fractions:

1. Lighters fraction: 123.95 g, mainly composed of unreacted methylamine (22 mol%), methanol (29 mol%) and ethanol (49 mol%): 80 mbar, head column T°C: 25°C.

2. Unreacted dimethyl 2-methyleneglutarate: 51.9 g, mainly composed of dimethyl 2-methyleneglutarate (84 mol%) and (IV) (16 mol%): 10 mbar, head column T°C: 104°C.

3. 1^st intermediate fraction: 12.03 g, mainly composed of dimethyl 2- m ethyleneglutarate (33 mol%) and (IV) (66 mol%): 5 mbar, head column T°C: 132°C.

4. 2^nd intermediate fraction: 32.60 g, mainly composed of dimethyl 2-methyleneglutarate (6 mol%) and (IV) (94 mol%): 6 mbar, head column T°C: 141°C.

5. Main fraction: 168.3 g, > 99 wt% of (IV): 5 mbar, head column T°C: 140°C. Residual water: 0.4 wt% (Karl-Fischer), base number: 0.005 meq/g.

After the distillation, around 35.3 g of an orange material was recovered in the boiler. ^JH NMR analysis shows that part of this residue is (IVa) and (IVb).

It is important to mention that the product (IV) is obtained here in the form of a mixture of (IVa) and (IVb) with (IVa) : (IVb) = 90 : 10 mol%. (IVb) is formed following a transesterification side-reaction with the ethanol solvent.

'H NMR (CDC1₃, 500 MHz) 5 (ppm): 4.00 (q, (IVb), 2H, J = 7.0 Hz), 3.55 (s, (IVa), 3H), 3.37 (dd, 1H, J = 12.3 Hz, 8.6 Hz), 3.30 (dd, 1H, J = 12.3 Hz, 5.2 Hz), 2.78 (s, 3H), 2.74-2.60 (m, 1H), 2.29 (dt, 1H, J = 17.8 Hz, 5.5 Hz), 2.20 (ddd, 1H, J = 17.8 Hz, 9.7 Hz, 5.9 Hz), 2.02-1.92 (m, 1H), 1.87-1.77 (m, 1H), 1.17 (t, (IVb), 3H, J = 7.0 Hz).

¹³C NMR (CDCI3, 126 MHz) 5 (ppm): 172.34 (IVa), 171.89 (IVb), 168.64 (IVb), 168.59 (IVa), 60.77 (IVb), 51.89 (IVa), 50.34 (IVb), 50.31 (IVa), 38.90 (IVb), 38.80 (IVa), 34.37, 30.31, 23.81, 13.91 (IVb). Example 2: Synthesis of compound (IVc) [compound (IV) with Ri = -nBu and R2 = -Me]

The precursor dimethyl 2-methyleneglutarate has been produced as described above.

The reaction was conducted under an inert argon atmosphere and in carefully dried vessel.

The tandem condensation/cyclization reaction has been conducted in a IL double jacketed reactor equipped with a mechanical stirrer (4 inclined plows stirrer devise with integrated baffles), a temperature probe, a condenser cooled at 7°C and a distillation apparatus connected to a 500 mL round bottom flask collector. The IL reactor was also connected to a pump through a Teflon pipe for the progressive addition of dimethyl 2-methyleneglutarate reactant.

In the IL reactor was loaded at room temperature: 127.5 g of n-butylamine (172.22 mL, 1.742 moles, 1 eq. with respect to dimethyl 2-methyleneglutarate) and the solution was stirred at 350 rpm at 20°C.

In a feeding flask connected to the addition pump through a Teflon line was loaded 300 g of dimethyl 2-methyleneglutarate (1.742 moles, 1 eq.).

The dimethyl 2-methyleneglutarate was then progressively added at room temperature thanks to the pump to the n-BuNLL solution over 40 minutes corresponding to a feeding flow of 7.5 g/min. Upon addition a very slight exothermy was observed with the temperature increasing only from 20°C to 20.6°C. After the end of the addition, the reaction mass was allowed to stir at 65°C during 2h30 allowing to reach approximately a conversion level of around 24 mol%. The reaction kinetic with n-butylamine was significantly slower than the kinetic observed with methylamine therefor the reaction mass temperature was further increased to 85-90°C and was stirred during 7h00. At this stage ^JH NMR analysis shows that the conversion level reached nearly 85 mol%.

The crude mixture was then distilled under vacuum in order to collect 5 main fractions:

1. Lighters fraction: 31 g, mainly composed of methanol (95 mol%) and n-BuNH2 (5 mol%): 100 mbar, head column T°C: 20°C.

2. Unreacted dimethyl 2-methyleneglutarate: 16.2 g, mainly composed of dimethyl 2-methyleneglutarate (85 mol%) and (IVc) (9 mol%) [the remaining component is anisole which is used as solvent during the synthesis of dimethyl 2-methyleneglutarate]: 20 mbar, head column T°C: 125°C. 3. 1^st intermediate fraction: 58.30 g, mainly composed of dimethyl 2- methyleneglutarate (45 mol%) and (IVc) (55 mol%): 5 mbar, head column T°C: 155°C.

4. 2^nd intermediate fraction: 30 g, mainly composed of dimethyl 2- methyleneglutarate (3 mol%) and (IVc) (97 mol%): 5 mbar, head column T°C: 156°C.

5. Main fraction: 245.8 g, > 99 wt% of (IVc): 3 mbar, head column T°C: 148°C. Residual water: 235 ppm (Karl-Fischer), base number: 0.005 meq/g.

After the distillation, around 27.6 g of a dark green material was recovered in the boiler. ^JH NMR analysis shows that part of this material consists of (IVc).

'H NMR (CDC1₃, 400 MHz) 5 (ppm): 3.66 (s, 3H), 3.46 (dd, 1H, J = 12.2 Hz, 8.8 Hz), 3.42-3.32 (m, 2H), 3.23 (dt, 1H, J = 13.5 Hz, 7.5 Hz), 2.98-2.68 (m, 1H), 2.42 (dt, 1H, J = 17.7 Hz, 5.8 Hz), 2.32 (ddd, 1H, J = 17.7 Hz, 9.6 Hz, 6.5 Hz), 2.12-2.02 (m, 1H), 1.98-1.84 (m, 1H), 1.54-1.35 (m, 2H), 1.25 (sext, 2H, J = 7.4 Hz), 0.86 (t, 3H, J = 7.3 Hz).

¹³C NMR (CDCI3, 101 MHz) 5 (ppm): 172.84, 168.58, 52.24, 48.62, 47.02, 39.30, 30.79, 29.15, 24.05, 20.18, 13.94.

Example 3: Synthesis of compound (IVd) [compound (IV) with Ri = -nHex and R2 = -Me].

The precursor dimethyl 2-methyleneglutarate has been produced as described above.

The reaction was conducted under an inert argon atmosphere and in carefully dried vessel.

The tandem condensation/cyclization reaction has been conducted in a IL double jacketed reactor equipped with a mechanical stirrer (4 inclined plows stirrer devise with integrated baffles), a temperature probe, a condenser cooled at 7°C and a distillation apparatus connected to a 500 mL round bottom flask collector. The IL reactor was also connected to a pump through a Teflon pipe for the progressive addition of dimethyl 2-methyleneglutarate reactant.

In the IL reactor was loaded at room temperature: 155.16 g of n- hexylamine (202.56 mL, 1.533 moles, 1 eq. with respect to dimethyl 2- methyleneglutarate) and the solution was stirred at 350 rpm at 20°C.

In a flask connected to the addition pump through a Teflon line was loaded 264 g of dimethyl 2-methyleneglutarate (1.533 moles, 1 eq.). The dimethyl 2-methyleneglutarate was then progressively added at room temperature thanks to the pump to the n-HexNH2 solution over 30 minutes corresponding to a feeding flow of 8.8 g/min. After the end of the addition, the reaction mass was allowed to stir at 90°C until the conversion level reached 85 mol% requiring around 7h00 of stirring at 90°C. The crude mixture was then distilled under vacuum in order to collect 4 main fractions:

1. Lighters fraction: 29.6 g, mainly composed of methanol: 30 mbar, head column T°C: 22°C.

2. Medium fraction composed of unreacted dimethyl 2- methyleneglutarate and n-hexylamine: 53.3 g, 3.5 mbar, head column T°C: 89°C.

3. Intermediate fraction: 7.7 g, mainly composed of dimethyl 2- methyleneglutarate (45 mol%) and (IVd) (55 mol%): 4.2 mbar, head column T°C: 152°C.

4. Main fraction: 219 g, > 99 wt% of (IVd): 3.5 mbar, head column T°C: 168°C. Residual water: 330 ppm (Karl-Fischer), base number: 0.005 meq/g.

After the distillation, around 84.3 g of brown-red residue remains in the boiler. ^JH NMR analysis shows that part of this material consists on (IVd).

'H NMR (CDC1₃, 400 MHz) 5 (ppm): 3.65 (s, 3H), 3.44 (dd, 1H, J = 12.4 Hz, 8.7 Hz), 3.40-3.29 (m, 2H), 3.21 (ddd, 1H, J = 13.3 Hz, 8.2 Hz, 6.9 Hz), 2.79-2.68 (m, 1H), 2.41 (dt, 1H, J = 17.8 Hz, 5.7 Hz), 2.32 (ddd, 1H, J = 17.8 Hz, 9.5 Hz, 6.5 Hz), 2.10-1.98 (m, 1H), 1.96-1.85 (m, 1H), 1.54-1.36 (m, 2H), 1.29 (brs, 6H), 0.80 (t, 3H, J = 7.0 Hz).

¹³C NMR (CDCI3, 101 MHz) 5 (ppm): 172.83, 168.55, 52.23, 48.62, 47.30, 39.29, 31.67, 30.78, 26.99, 26.61, 24.05, 22.63, 14.09.

Example 4: Synthesis of compound (IVe) [compound (IV) with Ri = -Me and R2 = -nHex].

The precursor dimethyl 2-methyleneglutarate has been produced as described above.

The reaction was conducted under an inert argon atmosphere and in carefully dried vessel.

The tandem condensation/cyclization reaction has been conducted in a IL double jacketed reactor equipped with a mechanical stirrer (4 inclined plows stirrer devise with integrated baffles), a temperature probe, a condenser cooled at 7°C and a distillation apparatus connected to a 500 mL round bottom flask collector. The IL reactor was also connected to a pump through a Teflon pipe for the progressive addition of dimethyl 2-methyleneglutarate reactant.

In the reactor was loaded at room temperature 191.21 g of a methylamine in ethanol solution (33 wt% methylamine concentration, 252.93 mL, 2.033 moles of methylamine, 1 eq.).

In a feeding tank connected to the pump through a Teflon pipe was added at room temperature 350 g of dimethyl 2-methyleneglutarate (2.033 moles, 1 eq.).

The amine solution in the reactor was stirred at 350 rpm and dimethyl 2- methyleneglutarate was then progressively added at room temperature into the reaction vessel over 40 minutes. Upon addition a very slight exothermy was observed.

At the end of the addition, the reaction mixture was allowed to stir at 50°C and the reaction progress was followed-up thanks to ^JH NMR analysis.

After 6h00 stirring at 50°C after the end of the addition, the conversion level of dimethyl 2-methyleneglutarate was about 85%.

The crude mixture was then distilled under vacuum in order to remove unreacted methylamine, co-produced methanol, ethanol solvent and unreacted dimer. At this stage 3 main fractions were obtained:

1^st light fraction: 179.9g mainly composed of 54 mol% of ethanol and 46 mol% of methanol [head column temperature: 39°C, 200 mbar] 2^nd light fraction: 1.6 g mainly composed of ethanol [head column temperature: 30°C, 80 mbar]

- 3^rd intermediate fraction: 71.5 g mainly composed of 65 mol% of unreacted dimer (II) and 35 mol% of (IVa + IVb) [head column temperature: 140°C, 5 mbar].

At this stage the residual level of dimer into the reaction mass was approximately 1 mol%.

The reaction mixture was then allowed to cool down to room temperature and 415.4 g of n-Hexanol was added (4.07 moles) followed by the addition of 24 g of methanesulfonic acid (0.250 mole) as catalyst. The reaction mixture was then allowed to stir at 100-120°C along with the progressive distillation of methanol and ethanol by-products until the conversion level to the desired hexyl ester reached 90 mol%.

The excess of hexanol was then distilled off under vacuum (100 mbar, 130°C in the reactor). The reaction mixture was then allowed to cool down to 60°C and 40 g of NaHCCh was then added (0.375 mole) into the reaction mass in order to neutralize the acid catalyst.

Finally the desired hexyl ester product was purified through vacuum distillation. At this stage 5 fractions were obtained:

1^st fraction: 37.8 g mainly composed of hexanol [head column temperature: 70°C, 30 mbar]

2^nd fraction: 55.5 g mainly composed of 94 mol% of hexanol and 6 mol% of dihexyl ether [head column temperature: 72°C, 4 mbar] 3^rd fraction: 17.4 g mainly composed of the desired product (IVe) and the intermediates (IVa) and (IVb) [head column temperature: 150°C, 3 mbar],

4^th fraction: 38.10 g mainly composed of the desired product (IVe) and the intermediates (IVa) and (IVb) [head column temperature: 160°C, 3 mbar],

5^th main fraction: 228.8 g mainly composed of the desired product (IVe) (92 mol%) and the intermediate (IVa) (4.5 mol%) [head column temperature: 171°C, 1.6 mbar].

Residual water in the main fraction: 460 ppm (Karl -Fischer), base number: 0.002 meq./g.

Example 5: Synthesis of a compound (IV) with Ri = cHex and Rz = -CH3 (IVf)

The precursor dimethyl 2-methyleneglutarate has been produced as described above.

The reaction was conducted under an inert argon atmosphere and in carefully dried vessel.

The conjugate addition/lactamization tandem reaction was conducted in a 1.5 L double jacketed reactor equipped with a mechanical stirrer (4 inclined plows stirrer device with integrated baffles), a temperature probe, a condenser cooled at 7°C, and a distillation bridge connected to a 500 mL round bottom flask collector.

In the reactor, the following were loaded at room temperature:

• 400 g of dimethyl 2-methyleneglutarate (2.32 moles, 1 eq.).

• 230.4 g of cyclohexylamine (2.32 moles, 1 eq.)

• 2.51 g of NaOMe (0.046 mole, 0.02 eq) The mixture was then allowed to stir (350 rpm) at 130°C, and the reaction progress was followed using 1H NMR spectroscopy. After 6 hours of stirring at 130°C, the conversion level of dimethyl 2-methyleneglutarate was about 84%. The reaction mixture was then allowed to cool down to 40°C, and the base catalyst was neutralized by the addition of 6.33 g of KHSO4 (0.046 mole, 1 eq. with respect to the base catalyst). After 30 minutes of stirring at 40°C, the crude mixture was then distilled under vacuum to collect 4 main fractions:

1. Lighters fraction: 68.27 g, mainly composed of methanol by-product: 200 mbar, head column T°C: 42°C.

2. Second lighters fraction: 41.10 g, mainly composed of methanol, unreacted cyclohexylamines, and dimethyl 2-methyleneglutarate: 6 mbar, head column T°C: 74°C.

3. Intermediate fraction: 46.60 g, mainly composed of unreacted dimethyl 2-methyleneglutarate and (IVf): 0.5 mbar, head column T°C: 153°C.

4. Main fraction: 306.9 g, mainly composed of the desired product (IVf) with 94 wt% purity (1H NMR): 0.5 mbar, head column T°C: 153°C.

After the distillation, around 158.5 g of a red viscous material was recovered in the boiler, which still contained around 88 wt% of undistilled (IVf).

Reaction yield: 84% [taking also into account the product (IVf) present in the intermediate fractions and in the boiler]. Dimethyl 2-methyleneglutarate conversion: 92% [based on recovered dimethyl 2-methyleneglutarate in the intermediate fractions]. Selectivity: 92%

1H NMR (CD3OD, 400 MHz) 5 (ppm): 4.38 (tt, 1H, J = 11.9 Hz, 4.1 Hz), 3.73 (s, 3H), 3.5 (d, 2H, J = 6.2 Hz), 2.98 - 2.84 (m, 1H), 2.48-2.36 (m, 2H), 2.14 - 1.94 (m, 2H), 1.92 - 1.80 (m, 2H), 1.74 - 1.35 (m, 7H), 1.25-1.12 (m, 1H). 13C NMR (CD30D, 101 MHz) 5 (ppm): 174.51, 171.28, 54.48, 52.70, 44.29, 40.05, 31.51, 30.53, 26.98, 26.71, 23.91.

Example 6: Active ingredients solubility tests.

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 at three different temperatures/conditions: 25°C, 0°C and 0°C + seeding.

The solutions were monitored during 1 week to watch for any active ingredient crystallization over ageing. 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 and during 48h00 at room temperature for the high loadings due to viscosity build-up. The solubilizing capabilities of each system was based on visual observations at room temperature, 0°C (1 week) and 0°C after seeding (1 week). Seeding corresponds to the addition of the smallest possible crystal of each active ingredient in the solution. It is performed in order to avoid supersaturation of actives ingredient. Addition of a crystal brings the sample back to the thermodynamical stability. 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.

With the compounds of the present invention and for some active ingredients [prothioconazole, tebuconazole and difenoconazole] a viscosity build-up was observed at high loadings limiting virtually the maximal solubility that can be truly reached. In other words this concentration limitation is therefore not due to a true solubility threshold as there is no precipitate observed and this viscosity issue can be mitigated by blending the solvent of the present invention with an additional solvent allowing potentially to reach even higher concentration compared to a standard polar solvent reference.

Globally, the highest active ingredient concentration we can achieve in a solvent, the most efficient the solvent is for this active ingredient.

The solubility results (i.e. the maximal solubility) at room temperature (r.t.) and at 0°C (+ seeding) for the solvent (IV) of the present invention obtained according to the example 1 (mixture of IVa and IVb, polar water miscible) is shown in the table 1 below along with the corresponding solubility data for the solvent Rhodiasolv® PolarClean (also polar water miscible) taken as the reference for a set of active ingredients. Similarly the solubility results at room temperature and at 0°C (+ seeding) for the solvent obtained according to example 3 (IVd, polar non water miscible) and for the solvent (IVf) obtained according to example 5 is shown in the table 2 below along with the corresponding solubility data for the solvent ADMA-10 (also polar non water miscible).

Table 1. Solubility at r.t. [and 0°C + seeding] in %w/v for (IVa+IVb) and PolarClean (R):

Table 2. Solubility at r.t. [and 0°C + seeding] in %w/v for (IVd), (IVf) and ADMA-10 (R):

Globally the data above show clearly that the solvents of the general formula (IV) display better solubility performances than the benchmarks, either for polar water miscible or polar non water miscible versions.

Claims

C L A I M S

1. The use of at least one N-alkyl 2-piperidinone 5-carboxylic acid ester of formula (IV):

(IV) wherein Ri and R2 are linear or branched or cyclic alkyl groups having from 1 to 12 C atoms, as solvent.

2. The use according to claim 1, wherein at least one of Ri and R2 is a methyl group.

3. The use according to claim 2, wherein Ri is methyl and R2 is a linear or branched or cyclic alkyl group having from 2 to 12 C atoms.

4. The use according to any of claims 1 to 3, wherein Ri is methyl and wherein at least 2 esters of formula (IV) are used as solvent.

5. The use according to claim 4, wherein the 2 esters are respectively the compound of formula (IV) with Ri = R2 = methyl (IVa) and the compound of formula (IV) with Ri = methyl and R2 = Ethyl (IVb).

6. The use according to any of claims 1 to 5, for the solubilization of agricultural active agents in agriculture formulations, preferably in DC formulations.

7. The use according to claim 2, wherein R2 is methyl and Ri is a linear or branched or cyclic alkyl group having from 2 to 12 C atoms, preferably from 5 to 12 C atoms, more preferably from 6 to 8 C atoms.

8. The use according to claim 7, for the solubilization of agricultural active agents in agriculture formulations, preferably in EC formulations.

9. An agriculture formulation (or agrochemical formulation) comprising an agricultural active compound and an ester of formula (IV) according to claim 1.

10. The agriculture formulation according to claim 9, comprising: a) at least one agricultural active compound; b) at least one ester of formula (IV) used as a solvent or co-solvent; c) optionally at least one emulsifier or/and one surfactant or/and dispersing agent; and d) optionally water.

11. The use of the agriculture formulation according to claim 9 or 10, for sustainable farming/cultivation.