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WO2025224139A1 - Dérivés de 2-pipéridinone et leur utilisation en tant que solvants - Google Patents

Dérivés de 2-pipéridinone et leur utilisation en tant que solvants

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Publication number
WO2025224139A1
WO2025224139A1 PCT/EP2025/061004 EP2025061004W WO2025224139A1 WO 2025224139 A1 WO2025224139 A1 WO 2025224139A1 EP 2025061004 W EP2025061004 W EP 2025061004W WO 2025224139 A1 WO2025224139 A1 WO 2025224139A1
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WIPO (PCT)
Prior art keywords
formulation
solvent
weight
agriculture
formula
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PCT/EP2025/061004
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English (en)
Inventor
Olivier BACK
Rawad TADMOURI
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Specialty Operations France SAS
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Specialty Operations France SAS
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Publication of WO2025224139A1 publication Critical patent/WO2025224139A1/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D211/74—Oxygen atoms
    • C07D211/76—Oxygen atoms attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D211/78—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Definitions

  • the present invention relates to 2-piperidinone derivatives (esters), and the use of the latter as solvents, more particularly as a polar aprotic solvent e.g. for the solubilization of agricultural active agents in agriculture formulations.
  • 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.
  • phytosanitary active agents fertilizers, pesticides
  • ECs emulsifiable concentrates
  • EC emulsifiable concentrates
  • EW concentrated emulsions in water
  • ME microemulsions
  • SE suspoemulsions
  • OD oil dispersions
  • DC dispersible concentrates
  • certain solid agricultural active compounds are often difficult to formulate.
  • 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.
  • 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.
  • 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.
  • N-methyl-2 -pyrrolidone (NMP) or N,N- dimethylacetamide are very common polar aprotic solvents that could be used for such application.
  • NMP N-methyl-2 -pyrrolidone
  • N,N- dimethylacetamide are very common polar aprotic solvents that could be used for such application.
  • 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.
  • 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.
  • it is not bio-sourced and there is still a need for molecules with improved solubility performance versus some compounds.
  • WO2012034689 relates to the use of 2-pyrrolidinone derivatives as solvents for agriculture formulations.
  • the compounds described in WO2012034689 display several drawbacks:
  • 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:
  • the manufacturing process can comprise 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) wherein R2’ is a linear or branched or cyclic alkyl group having from 1 to 12 C atoms different from R2.
  • 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).
  • 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.
  • the present invention concerns specific esters of formula (IV).
  • a pesticide means one pesticide or more than one pesticide.
  • solvent 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.
  • room temperature refers to a temperature of 20 to 30°C, typically to a temperature of 25°C.
  • 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.
  • nitrogen fertilizer stabilizer 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).
  • NBPT N-(n- butyl)thiophosphoric triamide
  • DCD dicyandiamide
  • 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).
  • 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).
  • urease inhibitors comprise NBPT, NPPT and CNPT (N-cyclohexylphosphoric triamide).
  • formulation 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).
  • % w/v“ refers to the weight amount of the respective ingredient based on a total volume of the formulation.
  • 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.
  • 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.
  • step 1. is conducted in the presence of a catalyst of formula (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.
  • Ra is a phenyl
  • R3 and R4 are ethyl
  • Rb is NRsRe with R5 and Re being ethyl.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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), dich
  • 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.
  • commonly used solvents are alcohols, for example methanol or ethanol, as solution of amines in alcohol solvents are commercially available.
  • 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.
  • basic compounds can be used as catalysts when employing bulky amines R1-NH2.
  • 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. . .
  • 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.
  • a suitable acid e.g. H2SO4, KHSO4, methanesulfonic acid etc..
  • the dimer of formula (II) can optionally be progressively added to the amine.
  • the amine reactant (III) can be progressively fed into the dimer of formula (II).
  • 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.
  • 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.
  • 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 R2’0H 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.
  • At least one of Ri and R2 is a methyl group.
  • Ri is methyl and R2 is a linear or branched or cyclic alkyl group having from 3 to 12 C atoms.
  • R2 is methyl and Ri is a linear or branched or cyclic alkyl group having from 5 to 12 C atoms.
  • 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 dilution in water during the use of the formulation and prevents the recrystallization of the active ingredient.
  • 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.
  • the present invention also relates to the use in EC formulations, of compounds according to the second preferred sub-embodiment of the invention as described above.
  • the present invention also relates to a process for the manufacture of molecules according to this second preferred sub-embodiment i.e. 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, preferably from 6 to 8 C atoms, more preferably nHex or cHex, said process involving the steps of
  • the head-to-tail catalytic dimerization step is preferably conducted according to the protocol described in the patents WO23066844 & WO23066829, the whole content of these applications being incorporated herein by reference for all purposes.
  • esters of formula (IV) as solvent, e.g. for the solubilization of agricultural active agents in agriculture formulations.
  • 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 derived the acrylate ester (I), is used during step 2 of the process of the invention i.e. the tandem amine condensation/cyclization or when a mixture of alcohols R2’0H is used during the optional transesterification step.
  • 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.
  • 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.
  • the present invention concerns the use of compounds of formula (IV) where R2 is a methyl group and Ri is a linear or branched or cyclic alkyl group having from 2 to 12 C atoms, as solvents.
  • 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.
  • 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.
  • 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.
  • NMP N-methyl-2 -pyrrolidone
  • NBP N-butyl-2 -pyrrolidone
  • Rhodiasolv® PolarClean Rhodiasolv® PolarClean
  • N,N-dimethyl lactamide Rhodiasolv® ADMA 10.
  • 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; and d) optionally water.
  • 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.
  • 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.
  • SDHIs succinate dehydrogenase inhibitors
  • the agricultural active compounds can be water-insoluble, at 20°C and at atmospheric pressure (i.e., 1.013xl0 5 Pa).
  • 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., 1.013xl0 5 Pa).
  • 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).
  • NBPT N-(n-butyl)thiophosphoric acid triamide
  • DCD dicyandiamide
  • said fertilizer formulation further comprises at least one biostimulant, one plant growth regulator, one natural plant defense enhancer and/or one inoculant.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • biostimulants include seaweed extracts (e.g., ascophyllum nodosum), humic acids (e.g., potassium humate), fulvic acids, myoinositol, glycine, and combinations thereof.
  • seaweed extracts e.g., ascophyllum nodosum
  • humic acids e.g., potassium humate
  • fulvic acids e.g., 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.
  • 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,
  • 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.
  • 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.
  • the agrochemical formulation according to the invention further comprises at least one surfactant.
  • the surfactants that may be used in the invention are chosen from anionic, non-ionic, cationic, amphoteric or zwitterionic surfactants, and mixtures thereof.
  • the surfactants are chosen from anionic surfactants, nonionic surfactants, and mixtures thereof.
  • 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).
  • 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,
  • 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.
  • phosphate ester groups 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) Cs-Cso, 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.
  • alkoxylated (ethoxylated, propoxylated, ethopropoxylated) groups and for which the sulfate functions appear in the free acid form, or are partly or totally neutralised.
  • 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-
  • 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.
  • non-ionic surfactants mention may be made without any intended limitation thereto, 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
  • sulfated ethoxylated tri-(phenyl-l-ethyl)phenol containing 16 oxy ethylene units
  • 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.
  • triglycerides of vegetable or animal origin.
  • 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.
  • 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.
  • polyalkoxylated ethoxylated, propoxylated, ethopropoxylated
  • CIO-C2O fatty acids such as lauric acid, stearic acid, or oleic acid
  • 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® V02003 a surfactant based on ethoxylated castor oil
  • Alkamuls® OL40 a surfactant based on ethoxylated sorbitan hexaoleate
  • Alkamuls® 1720 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.
  • 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.
  • 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.
  • 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:
  • 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;
  • 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;
  • 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.
  • - amines such as for example alkanolamines, morpholine ;
  • 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.
  • viscosity modifying agents 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,
  • 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.
  • the agriculture formulation according to the invention is in a liquid form, at 20°C and at atmospheric pressure (i.e., 1.013xl0 5 Pa) and may be in the form of a concentrate of agricultural active compound(s), a diluted concentrate, or a sprayable diluted.
  • formulations 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.
  • 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).
  • EW concentrated emulsions in water
  • ME microemulsions
  • SE suspoemulsions
  • OD oil dispersions
  • DC dispersions
  • SC suspension concentrates
  • CS capsule suspensions
  • SL soluble liquids
  • FS flowable concentrates for seed treatments
  • 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).
  • EC emulsifiable concentrate
  • EW concentrated emulsion in water
  • ME microemulsion
  • SE suspoemulsion
  • OD oil dispersion
  • DC dispersible concentrate
  • CS capsule suspension
  • SL soluble liquid
  • 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.
  • the agriculture formulation according to the invention is in the form of an emulsifiable concentrate (EC).
  • EC emulsifiable concentrate
  • 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.
  • 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).
  • the agrochemical formulation according to the invention is aqueous.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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).
  • polycondensates especially polyimides or polyesters or polyamides or polyamide-imides, especially partially or completely aromatic polycondensates such as aromatic polyamides (aramids).
  • ester of formula (IV) can be used as cleaning solvent for the cleaning of equipment like reactors for instance, in particular polymerization reactors.
  • 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.
  • the precursor dimethyl 2-methyleneglutarate has been produced starting from methyl acrylate according to the protocol described in the patents WO23066844 & WO23066829.
  • 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.
  • 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.
  • the conversion level of dimethyl 2-methyleneglutarate was about 47%.
  • 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%.
  • 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.
  • 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.
  • 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.
  • the dimethyl 2-methyleneglutarate was then progressively added at room temperature thanks to the pump to the n-BuNFB solution over 40 minutes corresponding to a feeding flow of 7.5 g/min.
  • a very slight exothermy was observed with the temperature increasing only from 20°C to 20.6°C.
  • 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.
  • J H NMR analysis shows that the conversion level reached nearly 85 mol%.
  • Lighters fraction 31 g, mainly composed of methanol (95 mol%) and n-BuNH2 (5 mol%): 100 mbar, head column T°C: 20°C.
  • 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.
  • 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:
  • Lighters fraction 29.6 g, mainly composed of methanol: 30 mbar, head column T°C: 22°C.
  • 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.
  • 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.
  • 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]
  • 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%.
  • 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.
  • 1 st fraction 37.8 g mainly composed of hexanol [head column temperature: 70°C, 30 mbar]
  • Residual water in the main fraction 460 ppm (Karl -Fischer), base number: 0.002 meq./g.
  • 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.
  • 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.
  • 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:
  • Lighters fraction 68.27 g, mainly composed of methanol by-product: 200 mbar, head column T°C: 42°C.
  • Second lighters fraction 41.10 g, mainly composed of methanol, unreacted cyclohexylamines, and dimethyl 2-methyleneglutarate: 6 mbar, head column T°C: 74°C.
  • 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.
  • 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.
  • 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.
  • the active ingredient 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.
  • solubility results i.e. the maximal solubility
  • 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
  • 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.
  • solubility results at room temperature and at 0°C (+ seeding) for the solvent (IVd) 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-IO (also polar non water miscible).

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Abstract

L'invention concerne des esters d'acide N-alkyl 2-pipéridinone 5-carboxylique, un procédé pour leur fabrication et leur utilisation en tant que solvant, par exemple pour la solubilisation d'agents actifs agricoles dans des formulations agricoles.
PCT/EP2025/061004 2024-04-24 2025-04-23 Dérivés de 2-pipéridinone et leur utilisation en tant que solvants Pending WO2025224139A1 (fr)

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PCT/EP2025/061004 Pending WO2025224139A1 (fr) 2024-04-24 2025-04-23 Dérivés de 2-pipéridinone et leur utilisation en tant que solvants
PCT/EP2025/061005 Pending WO2025224140A1 (fr) 2024-04-24 2025-04-23 Utilisation de dérivés de 2-pipéridinone en tant que solvants

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