USE OF ESTERAMIDES AS SOLUTIONS, ESTERAMIDES AS SUCH, AND METHOD FOR THE PREPARATION OF ESTERAMIDES

Description

[0001] The present invention relates to phytosanitary formulations using esteramide-type compounds as solvents.

[0002] Industry uses many chemical compounds as solvents, for example, to prepare chemicals and materials, to formulate chemical compounds, or to treat surfaces. For example, solvents are used in the formulation of plant protection products, particularly in the form of emulsifiable concentrates (ECs) intended to be diluted in water by the farmer before application to a field.

[0003] Industry is seeking new compounds to diversify or optimize products and processes that use solvents, particularly polar solvents. Specifically, industry needs compounds that are affordable and offer desirable performance properties. Industry also requires compounds with a favorable toxicological and / or environmental profile, including low volatility (low VOCs), good biodegradability, low toxicity, and / or low hazard.

[0004] The use of dialkylamides as solvents is well known. These are products with the formula R-CONMe2, where R is a hydrocarbon group such as an alkyl, typically C6-C30. Such products are notably marketed under the name Genagen® by Clariant. These solvents find applications particularly in the field of plant protection.

[0005] Dicarboxylic acid diesters are also known as solvents, particularly those obtained by esterification of a mixture of adipic acid, glutaric acid, and succinic acid. Such products are marketed under the names Rhodiasolv® RPDE and Rhodiasolv® DIB by the company Rhodia.

[0006] US patent application 4588833 (whose priority applications were published as DE 3339386 and DE 3420112) describes a process for preparing esteramides by high-temperature, cobalt-catalyzed reaction of an unsaturated amide with an alcohol and carbon monoxide. It also states that the prepared compounds can be used as polymer stabilizers. The esteramides prepared are as follows: Example 1 Mixture of A and B A: PhOOC-CH(CH 3 )-CH 2 -CONEt 2 B: PhOOC-CH 2 -CH 2 -CH 2 -CONEt 2 Examples 2-6 C: EtOOC-CH(CH 3 )-CH 2 -CONEt 2 Example 7 D: MeOOC-CH(CH 3 )-CH 2 -CONEt 2 Examples 8-9 E: Me-CH(OMe)-OOC-CH(CH 3 )-CH 2 -CONEt 2 Example 10 F: Cyclohexyl-OOC-CH(CH 3 )-CH 2 -CONEt 2 Example 11 G: Ph-CH 2 OOC-CH(CH 3 )-CH 2 -CONEt 2 (from the reagents) Example 12 H: p-cresyl-OOC-CH(CH 3 )-CH 2 -CONEt 2 Example 18-20 I: EtOOC-CHEt-CH 2 -CONEt 2 + J: EtOOC-CH(CH 3 )-CH 2 -CH 2 -CONEt 2 + K: EtOOC-CH 2 -CH 2 -CH 2 -CH 2 -CONEt 2

[0007] The compound with formula L:MeOOC-CHEt-CH 2 -CONMe 2 was identified by CAS Registry Number ®< 368212-04-8, in reference to document WO 01 / 79167 relating to a distant domain, and whose relevance is doubtful.

[0008] The compound with formula M: MeOOC-CH2-CH(CH3)-CH2-CONH(n-butyl) was identified by CAS Registry Number® 538326-02-2, in reference to a document relating to enzymatic reactions.

[0009] The compound with formula N:MeOOC-CH2-CH(CH3)-CH2-CONMe2 was identified by CAS Registry Number® 70367-41-8, in reference to a document concerning the implementation of lithium enolates.

[0010] US patent 3417114 describes in Example 9 the compound designated DMGME, with the formula O:MeOOC-CH₂-CH₂-CH₂-CONMe₂. This compound is prepared by reacting dimethyl glutarate with dimethylamine, then isolating DMGME by distillation from the resulting complex mixture (it is, in fact, a byproduct). DMGME is said to have a melting point of 7.5°C.

[0011] Document US 3288794 contains similar teachings.

[0012] US patent 4020099 mentions products such as DMGME and also refers to the crystallization of diphenyl terephthalate in solvents. However, DMGME is not used.

[0013] The compound with the formula P:MeOOC-CH2-CH2-CONMe2 was identified by CAS Registry Number® 30891-34-0, in reference to documents relating to distant domains, and whose relevance is questionable.

[0014] Document DE 1040234 describes the following compounds and their use as plasticizers: C 4 H 9 -OOC-CH 2 -CH 2 -CONEt 2 C 6 H 13 -OOC-(CH 2 ) 8 -CON(C 3 H 7 ) 2 C 8 H 17 -OOC-(CH 2 ) 8 -CON(C 4 H 9 ) 2 C 8 H 17 -OOC-(CH 2 ) 8 -CON(C 8 H 17 ) 2

[0015] As explained above, there remains a need for new solvents, particularly in plant protection formulations, and for new compounds. There is also a need for more efficient esteramide preparation processes.

[0016] The invention addresses at least one of the needs mentioned above by providing a concentrated plant protection product formulation comprising an active plant protection product and, as a solvent, an esteramide compound selected from the following compounds, and mixtures thereof: MeOOC-A MG -CONMe 2 MeOOC-A ES -CONMe 2 PeOOC-A MG -CONMe 2 PeOOC-A ES -CONMe 2 CycloOOC-A MG -CONMe 2 CycloOOC-A ES -CONMe 2 EhOOC-A MG -CONMe 2 EhOOC-A ES -CONMe 2 PeOOC-A MG -CONEt 2 PeOOC-A ES -CONEt 2 CycloOOC-A MG -CONEt 2 CycloOOC-A ES -CONEt 2 BuOOC-A MG -CONEt 2 BuOOC-A ES -CONEt 2 where A MG represents a group MG a of formula -CH(CH 3)-CH 2 -CH 2 -, or MG b of formula -CH 2 -CH 2 -CH(CH 3)- or a mixture of groups MG a and MG b A ES represents a group ES a of formula -CH(C 2 H 5 )-CH 2 -, or ES b of formula - CH 2 -CH(C 2 H 5 )- or a mixture of ES a and ES b groups Pe represents a pentyl group, Cyclo represents a cyclohexyl group, Eh represents a 2-ethylhexyl group, and Bu represents a butyl group. Definitions

[0017] In this application, the term solvent is understood in a broad sense, covering in particular the functions of co-solvent, crystallization inhibitor, and pickling agent. The term solvent may specifically refer to a product that is liquid at the temperature of use, preferably with a melting point of 20°C or lower, preferably 5°C, preferably 0°C, and that can contribute to liquefying a solid material, or to preventing or delaying the solidification or crystallization of a material in a liquid medium.

[0018] In this application, by " material composition", we mean a composition, more or less complex, comprising several chemical compounds. It may typically be an unpurified or modestly purified reaction product. The compound of the invention may, in particular, be isolated and / or commercialized and / or used in the form of a composition of matter comprising it. If the compound of the invention is a mixture of several compounds of formula (I), then it is also a composition of matter. The compound of the invention, in the form of a pure molecule or in the form of a mixture conforming to formula (I), may be included in a composition of matter.

[0019] In the composition of matter, the compound of the invention may represent at least 10% by weight. Preferably, it is the principal compound of the composition of matter. In this application, the principal compound is understood to be the compound with the highest content, even if its content is less than 50% by weight (for example, in a mixture of 40% A, 30% B, and 30% C, product A is the principal compound). Even more preferably, the compound of the invention represents at least 50% by weight of the composition of matter, for example, from 70 to 95% by weight, and even from 75 to 90% by weight. As indicated above, the composition of matter may be a reaction product. Composed of the invention (unclaimed)

[0020] The compound of the invention is a compound as listed in claim 1 and above. A "compound of the invention" should be understood as a compound implemented in the formulation according to the present invention.

[0021] According to an advantageous embodiment, the esteramide has a melting point less than or equal to 20°C, preferably 5°C, preferably 0°C. Process (unclaimed)

[0022] The compound of the invention can be prepared by any suitable method. In particular, a reaction step of an anhydride of formula (I') with an alcohol of formula R1<-OH and / or an amine of formula HNR2<R3<

[0023] The anhydride can be prepared in a preliminary step a) of cyclization of a diacid of formula HOOC-A-COOH, preferably by reaction of the diacid with acetic anhydride. In particular, refluxing in an excess of acetic anhydride can be carried out. Then, the product of formula (I') can be condensed.

[0024] In particular, one of the following reaction sequences 1) or 2) can be implemented: Sequence 1): Step 1b) the anhydride of formula (I') is reacted with an alcohol of formula R 1< -OH, so as to obtain an ester-acid compound of formula (I") R 1< -OOC-A-COOH, Step 1c) the compound of formula (I") is transformed into a compound of formula (I) using an amine of formula HNR 2< R 3< , Sequence 2): Step 2b) the anhydride of formula (I') is reacted with an amine of formula HNR 2< R 3< to obtain an amide-acid compound of formula (II") HOOC-A-CONR 2< R 3< (II'), Step 2c) the compound of formula (II") is transformed into a compound of formula (I) using an alcohol of formula R 1< -OH.

[0025] Step 1b) is preferably carried out using at least 1 molar equivalent of alcohol, relative to the anhydride. A large excess of alcohol can be used, for example from 2 to 20 equivalents, particularly from 5 to 15. Alcohol can be used as the solvent for the reaction.

[0026] According to a particular embodiment, step 1c) comprises the following steps (which may be simultaneous or subsequent, preferably subsequent): 1c1) the compound of formula (I") is transformed into an acyl chloride of the following formula (I‴), preferably by reaction with thionyl chloride, R 1< -OOC-A-COCI (I‴) 1c2) the compound of formula (I‴) is reacted with the amine of formula HNR 3< R 4< so as to obtain the compound of formula (I).

[0027] Step 1c2) is accompanied by the formation of hydrochloric acid. A base can be used to trap it, for example, triethanolamine or triethylamine (TEA). This step can be carried out with at least 0.8 molar equivalents of amine, preferably with at least one equivalent. An excess of 1.05 to 1.4 molar equivalents can be used.

[0028] According to another useful method for preparing the compound of the invention, a reaction step is carried out between a diester of formula R1<OOC-A-COOR1< and an amine of formula HNR2<R3<, followed optionally by a reaction step with an alcohol of formula R1'<-OH, where R1'< is a group selected from among the R1< groups mentioned above, but different from the R1< group of the diester. This method is particularly advantageous and economical because the diesters are prepared in large quantities and are readily available. It is thus possible to optimize production processes.For example, the following reaction sequence 3) can be implemented: Sequence 3) Step 3a) a diester of formula R 1< OOC-A-COOR 1< , preferably of formula MeOOC-A MG -COOMe or MeOOC-A ES -COOMe is reacted with an amine of formula HNR 2< R 3< so as to obtain a product comprising an esteramide of formula: R 1< OOC-A-CONR 2< R 3< , preferably R 1< OOC-A MG -CONR 2< R 3< or R 1< OOC-A ES -CONR 2< R 3< , preferably MeOOC-A MG -CONR 2< R 3< or MeOOC-A ES -CONR 2< R 3< .

[0029] Step 3b) Optionally, it is reacted with an alcohol of formula R 1'< -OH to obtain a product comprising an esteramide of formula R 1'< OOC-A-CONR 2< R 3< preferably R 1'< OOC-A MG -CONR 2< R 3< or R 1'< OOC-A ES -CONR 2< R 3< . where R 1'< is a group chosen from the R 1< groups mentioned above, but different from the R 1< group of the diester.

[0030] If the starting diester has the R1< group of the desired compound, then step 3b) is generally unnecessary. Otherwise, this step is typically implemented. Preferably, one starts with the diester having the desired R1< group.

[0031] In step 3a), preferably 0.7 to 1.5 moles of amine per mole of diester are used, for example 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles, preferably about 1 mole. It is advantageous to operate with a slight excess, such as at least 1.05 moles of amine per mole of diester, for example 1.05 to 1.1 moles of amine per mole of diester.

[0032] Step 3a) can be carried out in solution, for example in aqueous solution, or in solution in a solvent such as toluene or an alcohol. It is preferable to operate in a non-aqueous solution, avoiding the presence of any water. During this step, the methanol formed can be gradually removed to promote the reaction. This removal can be accompanied by the removal of the solvent, for example, to an azeotrope. After the methanol has been separated, the removed solvent can be reintroduced into the process. Step 3a) is preferably carried out in the presence of a catalyst, in particular a basic catalyst. Examples include methylates such as MeONa, carbonates such as K₂CO₃ and Na₂CO₃, and titanates.

[0033] Step 3b) is a transesterification step. It can be catalyzed by acids or bases, for example by K₂CO₃ or Na₂CO₃.

[0034] It should be noted that in all the processes and sequences mentioned above, optional intermediate separation and / or purification steps can be implemented to remove unwanted by-products. These by-products can then be used to manufacture other products or processed for reintroduction into the process.

[0035] The reaction may be followed by filtration and / or purification steps, for example by distillation.

[0036] Diacids, sometimes in the form of mixtures, can be obtained from a mixture of dinitrile compounds, sometimes also in the form of mixtures. The dinitriles may include dinitriles produced and recovered in the adiponitrile manufacturing process by double hydrocyanation of butadiene. In this case, they may be mixtures of dinitriles. This process, used on a large scale in industry to produce the vast majority of adiponitrile consumed worldwide, is described in numerous patents and publications.

[0037] The hydrocyanation reaction of butadiene leads mainly to the formation of linear dinitriles but also to the formation of branched dinitriles, the two main ones being methylglutaronitrile and ethylsuccinonitrile.

[0038] In the separation and purification stages of adiponitrile, the branched dinitrile compounds are separated by distillation and recovered, for example, as the head fraction in a distillation column.

[0039] Useful diacids can be obtained by reacting dinitrile compounds with a mineral base to produce acid salts, followed by neutralizing these salts with an acid. Useful diacids can also be obtained by acid hydrolysis of dinitrile compounds.

[0040] Diesters of formula R 1< OOC-A-COOR 1< useful for the implementation of sequence 3 are commercially available, notably from Invista under the references DBE, or from Rhodia under the name Rhodiasolv ®< RPDE.

[0041] Processes for the preparation of diacids and / or diesters are described in particular in documents WO2007 / 101929, FR 2902095, WO 2008 / 009792, WO 2008 / 062058. Uses (unclaimed) - Formulations

[0042] The compound of the invention and / or a composition of material comprising it described above can, in particular, be used in plant protection formulations comprising a solid active ingredient. Further details are given below, where the word "solvent" may refer to the compound of the invention or a composition of material comprising it, as described above. Detailed use in plant protection formulations

[0043] A plant protection formulation is generally a concentrated plant protection formulation comprising an active compound.

[0044] Agriculture uses many active ingredients such as fertilizers and pesticides, for example, insecticides, herbicides, and fungicides. These are referred to as active plant protection products (or active ingredients). Active plant protection products are generally produced in pure or highly concentrated form. They must be used on farms at low concentrations. To this end, they are usually formulated with other ingredients to allow for easy dilution by weight by the farmer. These are called plant protection formulations. The dilution carried out by the farmer is generally achieved by mixing the plant protection formulation with water.

[0045] Therefore, plant protection product formulations must allow for easy dilution by weight by the farmer to obtain a product in which the plant protection product is properly dispersed, for example, as a solution, emulsion, suspension, or superemulsion. Plant protection product formulations thus allow for the transport of a plant protection product in a relatively concentrated form, easy packaging, and / or easy handling for the end user. Different types of plant protection product formulations can be used depending on the specific plant protection product. Examples include emulsifiable concentrates (EC), concentrated emulsions (EW), microemulsions (ME), wettable powders (WP), and water-dispersible granules (WDG).The formulations that can be used depend on the physical form of the plant protection product (for example, solid or liquid), and on its physico-chemical properties in the presence of other compounds such as water or solvents.

[0046] After dilution by weight by the farmer, for example by mixing with water, the plant protection product can be found in various physical forms: solution, dispersion of solid particles, dispersion of product droplets, droplets of the solvent in which the product is dissolved, etc. Plant protection formulations generally include compounds that allow these physical forms to be obtained. These may include, for example, surfactants, solvents, mineral carriers, and / or dispersants. Often, these compounds are not active ingredients but rather intermediates that aid in the formulation. Plant protection formulations can be in liquid or solid form.

[0047] To prepare plant protection product formulations of solid active ingredients, it is common practice to solubilize the product in a solvent. The resulting formulation thus comprises a solution of the product in the solvent. The formulation can be in solid form, for example, as a wettable powder (WP) where the solution saturates an inorganic support, such as kaolin and / or silica. Alternatively, the formulation can be in liquid form, for example, as an emulsifiable concentrate (EC) consisting of a single clear liquid phase comprising the solvent and the product in solution, which can form an emulsion upon the addition of water, with or without gentle stirring. It can also be in the form of a concentrated emulsion (EW), which is cloudy, and in which the phase dispersed in water comprises the solvent and the product in solution within the solvent.It can also be in the form of a clear microemulsion (ME), the phase of which dispersed in water includes the solvent and the product in solution in the solvent.

[0048] Some solid plant protection products are often difficult to formulate. For example, tebuconazole is a particularly effective fungicide, widely used especially in soybean cultivation. For some plant protection products, it is difficult to create concentrated formulations that are easy for farmers to dilute, stable, and without substantial (proven or perceived) drawbacks in terms of safety, toxicity, and / or ecotoxicity. For some products, it is difficult to formulate at relatively high concentrations with sufficient stability. In particular, it is necessary to prevent the formation of crystals, especially at low temperatures and / or during dilution and / or during storage of the diluted composition at high temperatures.Crystals can have negative effects, including clogging filters of devices used to spread the diluted composition, clogging spraying devices, decreasing the overall activity of the formulation, creating unnecessary waste stream problems to dispose of the crystals, and / or causing poor distribution of the active product on the agricultural field.

[0049] Formulations containing the solvent notably include: solubilization of large quantities of active ingredients, absence of crystallization, even under demanding conditions, good biological activity which may be due to good solvation, and / or a safety, toxicology and / or ecotoxicology profile perceived as favorable.

[0050] The plant protection product formulation may also be a concentrated plant protection product formulation comprising: a) an active plant protection product, b) the solvent (esteramide compound) c) possibly at least one emulsifying agent, preferably a surfactant, and d) possibly water. active plant protection product a)

[0051] Active plant protection products, including water-insoluble and solid products, are known to those skilled in the art. An active plant protection product may be a herbicide, an insecticide, an acaricide, a fungicide, or a rodenticide, for example, a rat poison.

[0052] As non-limiting examples of suitable active ingredients, the following may be cited, among others: Ametrine, Diuron, Linuron, Chlortoluron, Isoproturon, Nicosulfuron, Metamitron, Diazinon, Aclonifen, Atrazine, Chlorothalonil, Bromoxynil, Bromoxynil heptanoate, Bromoxynil octanoate, Mancozeb, Maneb, Zineb, Phenmedipham, Propanyl, the phenoxyphenoxy series, the heteroaryloxyphenoxy series, CMPP, MCPA, 2,4-D, Simazine, the active ingredients of the imidazolinone series, the organophosphate family, including Azinphos-ethyl, Azinphos-methyl, Alachlor, Chlorpyrifos, Diclofop-methyl, Fenoxaprop-p-ethyl, Methoxychlor, Cypermethrin, Fenoxycarb, cymoxanil, chlorothalonyl, Ikes neonicotinoid insecticides, the triazole fungicide family such as azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxyconazole, fenbuconazole, flusilazole, myclobutanyl,tebuconazole, triadimefon, triadimenol, strobilurins such as pyraclostrobin, picoxystrobin, azoxystrobin, famoxadone, kresoxym-methyl and trifloxystrobin, solfonylureas such as bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, metsulfuron-methyl, nicosulfuron, sulfomethuron-methyl, triasulfuron, tribenuron-methyl.,

[0053] We choose the non-water-soluble products from this list.

[0054] The following active plant protection products can be used: Alachlor Chlorpyrifos alpha-cypermethrin In racemic mixtures and / or as isolated stereoisomers. Phenmedipham Propane Pendimethalin triadimenol Trifluralin Oxyfluorfen Dimethoate Imidacloprid Proxopur Benomyl Deltamethrin Fenvalerate Abamectin Amicarbazone Bifenthrin Carbosulfan Cyfluthrin Difenconazole Ethofenprox Fenoxaprop-ethyl Fipronil Fenvalerate Fluazifop-p-butyl Flufenouron Hexazinone Lambda-cyalothrin Methomyl Permethrin Prochloraz Propiconazole Tebuconazole

[0055] These products and names are familiar to those skilled in the art. Several active plant protection products can be combined. Emulsifying agent c)

[0056] The plant protection formulation may include an emulsifying agent, typically and preferably a surfactant. Emulsifying agents are agents intended to facilitate emulsification or dispersion after the formulation has been brought into contact with water, and / or to stabilize (over time and / or temperature) the emulsion or dispersion, for example by preventing sedimentation.

[0057] Surfactants are known compounds with a generally relatively low molar mass, for example, less than 1000 g / mol. A surfactant can be anionic (in its saline or acidic form), nonionic (preferably polyalkoxylated), cationic, or amphoteric (a term that also includes zwitterionic surfactants). It can also be a mixture or a combination of these surfactants.

[0058] Examples of anionic surfactants include, but are not limited to: alkylsulfonic acids, arylsulfonic acids, possibly substituted by one or more hydrocarbon groups, and whose acid function is partially or totally salified, such as C8-C50 alkylsulfonic acids, more particularly C8-C30, preferably C10-C22, benzenesulfonic acids, naphthalenesulfonic acids, substituted by one to three alkyl groups in C1-C30, preferably C4-C16, and / or alkenyl groups in C2-C30, preferably C4-C16. the mono- or diesters of alkylsulfosuccinic acids, the alkyl part of which, linear or branched, may be substituted by one or more hydroxylated and / or alkoxylated groups, linear or branched in C2-C4 (preferably ethoxylated, propoxylated, ethopropoxylated).Phosphate esters, chosen particularly from those comprising at least one saturated, unsaturated, or aromatic hydrocarbon group, linear or branched, comprising 8 to 40 carbon atoms, preferably 10 to 30, optionally substituted by at least one alkoxylated group (ethoxylated, propoxylated, ethopropoxylated). Furthermore, they comprise at least one phosphate ester group, mono- or diesterified such that one or two free acid groups, or partially or totally salified acid groups, may be present.Preferred phosphate esters are of the type of mono- and diesters of phosphoric acid and alkoxylated mono-, di- or tristyrylphenol (ethoxylated and / or propoxylated), or alkoxylated mono-, di- or trialkylphenol (ethoxylated and / or propoxylated), optionally substituted by one to four alkyl groups; of phosphoric acid and a C8-C30, preferably alkoxylated C10-C22 (ethoxylated or ethopropoxylated) alcohol; of phosphoric acid and a non-alkoxylated C8-C22, preferably C10-C22, alcohol. sulfate esters obtained from saturated or aromatic alcohols, possibly substituted by one or more alkoxylated groups (ethoxylated, propoxylated, ethopropoxylated), and for which the sulfate functions are present in the free acid form, or partially or totally neutralized.For example, we can cite sulfate esters obtained more particularly from C8-C20 alcohols, saturated or unsaturated, which can include 1 to 8 alkoxylated motifs (ethoxylated, propoxylated, ethopropoxylated); sulfate esters obtained from polyalkoxylated phenol, substituted by 1 to 3 C2-C30 hydroxycarbon groups, saturated or unsaturated, and in which the number of alkoxylated motifs is between 2 and 40; sulfate esters obtained from polyalkoxylated mono-, di- or tristyrylphenol in which the number of alkoxylated motifs varies from 2 to 40.

[0059] Anionic surfactants can be in acidic form (they are potentially anionic), or in a partially or totally salted form, with a counter-ion. The counter-ion can be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or an ammonium ion of the formula N(R)4+, in which R, identical or different, represents a hydrogen atom or a C1-C4 alkyl radical possibly substituted by an oxygen atom.

[0060] Examples of non-ionic surfactants include, but are not limited to: Polyalkoxylated phenols (ethoxylated, propoxylated, ethopropoxylated) substituted by at least one alkyl radical in C4-C20, preferably in C4-C12, or substituted by at least one alkylaryl radical whose alkyl portion is in C1-C6. More specifically, the total number of alkoxylated motifs is between 2 and 100. Examples include mono-, di- or tri(phenylethyl) polyalkoxylated phenols, or polyalkoxylated nonylphenols.Among the ethoxylated and / or propoxylated, sulfated and / or phosphated di- or tristyrylphenols, we can mention: ethoxylated di-(1-phenyl)phenol, containing 10 oxyethyl groups; ethoxylated di-(1-phenyl)phenol, containing 7 oxyethyl groups; sulfated ethoxylated di-(1-phenyl)phenol, containing 7 oxyethyl groups; ethoxylated tri-(1-phenyl)phenol, containing 8 oxyethyl groups; ethoxylated tri-(1-phenyl)phenol, containing 16 oxyethyl groups; sulfated ethoxylated tri-(1-phenyl)phenol, containing 16 oxyethyl groups; ethoxylated tri-(1-phenyl)phenol, containing 20 oxyethyl groups; ethoxylated tri-(1-phenyl)phenol Phosphated, containing 16 oxyethylenated units. Alcohols or C6-C22 fatty acids, polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated). The number of alkoxylated units is between 1 and 60.The term ethoxylated fatty acid includes both products obtained by ethoxylation of a fatty acid with ethylene oxide and those obtained by esterification of a fatty acid with polyethylene glycol. It also includes polyalkoxylated triglycerides (ethoxylated, propoxylated, ethopropoxylated) of plant or animal origin. This includes triglycerides derived from lard, tallow, peanut oil, butter oil, cottonseed oil, linseed oil, olive oil, palm oil, grapeseed oil, fish oil, soybean oil, castor oil, rapeseed oil, copra oil, coconut oil, and comprising a total number of alkoxylated motifs between 1 and 60. The term ethoxylated triglyceride refers both to products obtained by ethoxylation of a triglyceride with ethylene oxide and to those obtained by transesterification of a triglyceride with polyethylene glycol.sorbitan esters possibly polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated), more particularly cyclized sorbitol esters of C10 to C20 fatty acids such as lauric acid, stearic acid or oleic acid, and comprising a total number of alkoxylated motifs between 2 and 50.

[0061] Useful emulsifiers include the following products, all marketed by Rhodia: Soprophor® < TSP / 724: ethopropoxylated tristyrylphonol-based surfactant Soprophor® < 796 / O: ethopropoxylated tristyrylphonol-based surfactant Soprophor® < CY 8: ethoxylated tristyrylphonol-based surfactant Soprophor® < BSU: ethoxylated tristyrylphonol-based surfactant Alkamuls® < RC: ethoxylated castor oil-based surfactant Alkamuls® < OR / 36: ethoxylated castor oil-based surfactant Alkamuls® < T / 20: sorbitan ester-based surfactant

[0062] The formulation advantageously comprises at least 4%, preferably at least 5%, preferably at least 8%, by weight of dry matter, of at least one surfactant (c).

[0063] It is mentioned that the solvent can be associated with an aromatic and / or non-aromatic surfactant. Further details regarding the phytosanitary formulation

[0064] The concentrated plant protection product formulation preferably does not contain significant amounts of water. Typically, the water content is less than 50% by weight, advantageously less than 25% by weight. It will generally be less than 10% by weight.

[0065] The formulation is preferably a liquid formulation, for example in the form of an emulsifiable concentrate (EC), a concentrated emulsion (EW), or a microemulsion (ME). In this case, it preferably contains less than 500 g / L of water, and more preferably less than 250 g / L. It will generally be less than 100 g / L.

[0066] The formulations may advantageously include: a) 4 to 60%, preferably 10 to 50%, of the plant protection product, by weight of active material, b) 10 to 92%, preferably 20 to 80%, of the solvent, by weight, c) 4 to 60%, preferably 5 to 50%, preferably 8 to 25%, by weight of dry matter, of an emulsifier, preferably a surfactant, d) 0 to 10% by weight of water.

[0067] It is not excluded to produce solid formulations, for example formulations in which a liquid comprising the plant protection product solubilized in the solvent, is supported by a mineral and / or dispersed in a solid matrix.

[0068] The formulation may, of course, include ingredients (or "other additives") other than the active plant protection product, the solvent(s), the optional emulsifying agent(s), and optional water. It may, in particular, include viscosity-modifying agents, antifoaming agents (including silicone-based antifoams), anti-rebound agents, anti-wash-off agents, inert fillers (including mineral fillers), antifreeze agents, etc.

[0069] In particular, formulations may include additives, referred to as other additives, not included in the definition of products a), b), or c), such as: Other solvents, generally in small quantities, for example, in quantities less than the amount of compound of formula (I). Examples of other solvents include phosphate, phosphonate, and phosphine oxide solvents such as TEBP, TBP, TEPO, and DBBP. Also included are alkyldimethylamides where the alkyl group is at the C6-C18 position, particularly those marketed under the Genagen brand. Other examples include ester lactates, particularly those marketed under the Purasolv brand. Fatty acid methyl esters, particularly those marketed under the Phytorobe brand, are also included. Finally, diacid diesters ("DiBasic Esters"), particularly those marketed by Rhodia under the Rhodiasolv RPDE and Rhodiasolv DIB brands, are also included. Hydrocarbon fractions, cyclic amides such as NMP, and lactones are also mentioned. Bis(dialkylamides) described in document WO 2008 / 074837 are also cited.Crystallization inhibitors. These may include the solvents mentioned above. They may also include non-polyalkoxylated fatty acids or fatty alcohols. For example, the product Alkamuls® OL700, marketed by Rhodia, is cited.

[0070] Conventional methods for preparing plant protection product formulations or solvent mixtures can be used. This can be done by simply mixing the components.

[0071] The concentrated plant protection product formulation is intended to be applied to a cultivated field or a field to be cultivated, for example, a soybean field, most often after dilution in water to obtain a diluted composition. The dilution is generally carried out by the farmer directly in a tank ("tank-mix"), for example, in the tank of a device designed to spread the composition. The farmer may add other plant protection products, such as fungicides, herbicides, pesticides, insecticides, or fertilizers. Thus, the formulation can be used to prepare a diluted composition of the active plant protection product in water by mixing at least one part by weight of the concentrated formulation with at least 10 parts water, preferably less than 1000 parts.Dilution rates and quantities to be applied to the field generally depend on the plant protection product and the desired dose to treat the field; this can be determined by the farmer.

[0072] Other details or advantages may become apparent from the examples that follow. EXAMPLES General procedures implemented for the synthesis of esteramides Procedure A : Formation of the acid ester

[0073]

[0074] The cyclic anhydride is mixed with alcohol and heated to 60°C for 3 hours. Volatile compounds are removed by distillation under reduced pressure if necessary. The final product can be purified by distillation under reduced pressure. Procedure B Formation of the acid ester / chloride

[0075]

[0076] The ester / acid and thionyl chloride are mixed at room temperature. The reaction mixture can be heated under reflux to complete the reaction. Volatile species are removed by distillation under reduced pressure to obtain the crude product, which is typically used as is without further purification. Procedure C Ester / amide formation

[0077]

[0078] Toluene and trimethylamine (TEA) are mixed under an inert atmosphere and cooled to -20°C. Dimethylamine (DMA) is then added. The acid ester / chloride is added slowly to maintain the temperature below 0°C. The mixture is then stirred at room temperature overnight and filtered to remove the precipitate. The filtrate is evaporated under vacuum to obtain the crude product. The final product is obtained by distillation of the crude reaction mixture under reduced pressure. Procedure D : Formation of acid amide

[0079]

[0080] Cyclic anhydride is added to the primary amine while maintaining the temperature below 40°C. The mixture is then kept at room temperature for 10–24 hours. Volatile species are evaporated under vacuum. The product can be purified by distillation under reduced pressure. Procedure E Formation of esteramide

[0081]

[0082] The acid amide and alcohol are mixed at room temperature, and then thionyl chloride is added slowly to maintain the temperature below 30°C. The hydrochloric acid formed during the reaction can be trapped by a concentrated sodium hydroxide solution. The reaction mixture is stirred at room temperature until the starting materials have been consumed. The reaction can be monitored by GC. Volatile species are evaporated under vacuum to obtain the crude product. In some cases, the crude product is dissolved in methanol, and the pH is adjusted to around 6–7 before solvent evaporation. The final product is then obtained by distillation under reduced pressure. Procedure F - Preparation of 2-MGA cyclic anhydride

[0083] Raw materials

[0084] 2-Methylglutaric acid (2-MGA) Acetic anhydride 327g; 2.23mol; Mw: 146.14 500ml; 4.9mol; 2.2eq. MW: 102.09

[0085] Pure 2-MGA and acetic anhydride are mixed and heated under reflux (140°C) for 7 hours. The excess acetic anhydride and the acetic acid formed are evaporated under vacuum to obtain the crude reaction product (320 g). The resulting oil is distilled under reduced pressure (120°C / 310 Pa) to obtain a white solid (263 g). Yield = 92.2% Example 1.1 - Preparation of MeOOC-CH 2 -CH 2 -CONM e2 (unclaimed) The synthesis method is as follows:

[0086] Step 1 : Raw materials

[0087] Cyclic anhydride Methanol (anhydrous) 250g; 2.473mol; MW: 100.07; 99% 1000ml; 24.73mol, Mw: 32.04; 10eq

[0088] The acid ester is obtained by Procedure A.

[0089] Final product = 311g, Yield = 94%

[0090] Analysis by GC (gas chromatography): surface > 99% Step 2 Raw materials

[0091] Ester / acid Thionyl chloride 311g; 2.331mol; MW: 132.11; GC: (area) = 99.03% 340ml; 4.662mol; Mw: 118.97, 2eq

[0092] The acid ester / chloride is obtained by Procedure B.

[0093] Gross product = 348g Step 3 Raw materials

[0094] Acid ester / chloride DMA TEA Toluene 348g; 2.311 mol; 1eq. MW: 150.56 280ml; 4.22mol, 1.83eq, Mw: 45.08 390ml; 2.80mol, 1.2eq; Mw:101.2 1750+500ml

[0095] The ester / amide ester obtained by Procedure C.

[0096] Gross product = 402g

[0097] Final product = 218g

[0098] CG analysis (surface) > 98% Example 1.2 - Preparation of MeOOC-CH 2 -CH 2 -CH 2 -CONMe 2 (unclaimed)

[0099] The synthesis method is as follows: Step 1 Raw materials

[0100] Cyclic anhydride Methanol 257g; 2.2mol; 1eq. MW: 114.10; (GC: 97.89%) 4350ml; 107.4mol; 48.8eq. MW: 32.04

[0101] The acid ester is obtained by Procedure A.

[0102] Gross product = 333g (yellow liquid)

[0103] Final product = 274g

[0104] Analysis by GC (gas chromatography): surface > 99% Step 2 Raw materials

[0105] acid ester Thionyl chloride 274g; 1.869mol; 1eq. MW: 114.10; (GC: 99.68%) 273ml; 3.738mol; 2eq. MW: 118.97

[0106] The acid ester / chloride is obtained by Procedure B.

[0107] Gross product = 314g (red liquid), Yield >99% Step 3 Raw materials

[0108] Acid ester / chloride DMA TEA Toluene 314g; 1.869mol; 1eq. Mw:164.59 (if 100%) 250ml; 3.738mol, 2eq, Mw: 45.08; d=0.68 227ml; 2.243mol, 1.2eq, Mw: 101.19; d=0.726 1250+500ml

[0109] The ester / amide ester obtained by Procedure C.

[0110] Gross product = 339g

[0111] Final product = 237g, Yield = 89.6%

[0112] CG analysis (surface) > 99% Example 1.3 - Preparation of MeOOC-A MG -CONMe 2 The first method of synthesis is as follows:

[0113] Step 1 Raw materials

[0114] Cyclic anhydride methanol 245g; 1.91mol; MW: 128.13; GC > 99% 1500ml

[0115] The anhydride is obtained by Procedure F.

[0116] The acid ester is obtained by Procedure A.

[0117] Gross product = 302g

[0118] Final product = 261g, Yield = 85.6%

[0119] GC (gas chromatography) analysis: surface area > 99% (isomers 58 / 42) Step 2 Raw materials

[0120] Ester / acid Thionyl chloride 261g; 1.432mol, Mw: 160.17, 240ml; 2.86mol; 2eq. MW: 118.97

[0121] The acid ester / chloride is obtained by Procedure B.

[0122] Gross product = 290g (yellow liquid) Step 3 Raw materials

[0123] Acid ester / chloride DMA TEA Toluene 290g; 1.62mol; Mw: 178.61 218ml; 3.24mol, 2eq; MW: 45.08 284ml; 2.02mol; 1.25eq; MW: 101.19 2000ml

[0124] Methyl ester dimethyl amide is obtained by Procedure C.

[0125] Gross product = 303g (red liquid)

[0126] Final product, GC analysis (surface) > 99% (isomers 63 / 37) Example 1.4 - Preparation of MeOOC-A MG -CONMe2 by a second route The synthesis route is as follows:

[0127] Step 1 Raw materials

[0128] Cyclic anhydride DMA aq. 264g; 2.06mol; 1eq. MW: 128.13; GC (surface) >99% 1000 ml; 6.84 mol; 3 eq. Mw: 45.08; 33% in water

[0129] The anhydride is obtained by Procedure F.

[0130] The acid amide is obtained according to procedure D.

[0131] Raw product = 368g (red oil) (isomers 29 / 71) Step 2 Raw materials

[0132] amide-acid Methanol Thionyl chloride 236 g; 1.36 mol; 1 Eq Mw: 173.21 2360ml; Mw: 32.04 236ml; 3.25mol; 2.4eq; MW: 118.97; 99%

[0133] Methyl ester dimethyl amide is obtained according to Procedure E.

[0134] Raw product = 300g

[0135] Final product = 171g, Yield = 68%

[0136] CG analysis (surface) > 99% (isomers 31 / 69) Example 1.5 - Préparation de Isoamyl-OOC-A MG CONMe 2(not claimed) The synthesis route is as follows (only the major species are represented):

[0137]

[0138] A crude mixture called "MGN" is hydrolyzed, consisting mainly of 2-methylglutaroinitrile (2-MGN), ethylsuccinonitrile (ESN), and adiponitrile (ADN), to obtain a mixture called MGA : Mixture comprising 2-methylglutaric acid (86% by moles), ethyl succinic acid (11% by moles) and adipic acid (3% by moles)

[0139] We carry out a transformation into anhydride according to procedure F.

[0140] The following steps are then carried out: Step 1 Raw materials

[0141] Cyclic anhydride DMA aq. 780 g; 6.09 mol; 1 Eq 2500mL; 16.31mol; 2.6.eq. Mw: 128.13; GC (surface) >99% Mw: 45.08; 33% in water

[0142] The acid amide is obtained according to procedure D.

[0143] Raw product = 1120g (yellow liquid) (isomers 29 / 71) Step 2 Raw materials

[0144] amide-acid 3-methyl-1-butanol Thionyl chloride 1510 g; 8.2 mol; 1 Eq 2869 ml; 25.7 mol; 3.2 Eq 1446 mL; 19.69 mol; 2.5 eq Mw: 173.21 Mw: 88.15 Mw: 118.97; 99%

[0145] Dimetheyl amide ester is obtained according to Procedure E.

[0146] Raw product = 300g

[0147] Final product = 1242g (Boiling point ~ 132° / 70Pa)

[0148] CG analysis (surface) > 96% (isomers 31 / 69)

[0149] The details of the CG analysis are given below. Compound CG (surface) 54,72% 21,25% 5,11% 2,75 % 0,59% Diester(s) 14,97% Example 1.6 - Preparation of cyclohexyl-OOC-A MG-CONMe 2

[0150]

[0151] A crude mixture called "MGN" is hydrolyzed, consisting mainly of 2-methylglutaroinitrile (2-MGN), ethylsuccinonitrile (ESN), and adiponitrile (ADN), to obtain a mixture called MGA: Mixture comprising 2-methylglutaric acid (86% by moles), ethyl succinic acid (11% by moles) and adipic acid (3% by moles)

[0152] We carry out a transformation into anhydride according to procedure F.

[0153] The following steps are then carried out: Step 1 Raw materials

[0154] Cyclic anhydride DMA aq. 331 g; 2.58 mol; 1 Eq 1030mL; 6.72mol; 2.6 eq. Mw: 128.13; GC (surface) >99% Mw: 45.08; 33% in water

[0155] The acid amide is obtained according to procedure D.

[0156] Raw product = 440g (yellow liquid) (isomers 29 / 71), >94.7% GC Step 2 Raw materials

[0157] Acid amide Cyclohexanol Thionyl chloride 400 g; 2.31 mol; 1 Eq 289 g; 1.25 mol Eq 302 g; 2.54 mol; 1.1 eq Mw: 173.21 Mw: 100 Mw: 118.97; 99%

[0158] The dimethyl amide ester is obtained according to Procedure E except that the acid amide is dissolved in dichloromethane before the reaction.

[0159] Final product = 430g (Boiling point ~ 140-144°C / 40Pa), % Yield = 73%, GC analysis (surface) > 97%

[0160] The details of the CG analysis are given below. Compound CG (surface) 52.05% 33.71% 7.47% 2.95% 0.83% 1.41% 0.75% Example 1.7 - Preparation of 2-ethylhexyl-OOC-A MG-CONMe 2

[0161]

[0162] A crude mixture called "MGN" is hydrolyzed, consisting mainly of 2-methylglutaroinitrile (2-MGN), ethylsuccinonitrile (ESN), and adiponitrile (ADN), to obtain a mixture called MGA : Mixture comprising 2-methylglutaric acid (86% by moles), ethyl succinic acid (11% by moles) and adipic acid (3% by moles)

[0163] We carry out a transformation into anhydride according to procedure F.

[0164] Next, procedure D is carried out.

[0165] The following steps are then carried out: Step 1 Raw materials

[0166] Acid amide 2-Ethylhexanol Thionyl chloride 350 g; 2.02 mol; 1 Eq 395 mL; 2.53 mol; 1.25 Eq 160 mL; 2.22 mol; 1.1 eq Mw: 173.21 Mw: 130 Mw: 118.97; 99%

[0167] The dimethyl amide ester is obtained according to Procedure E except that the acid amide is dissolved in dichloromethane before the reaction.

[0168] Final product = 308g (Boiling point ~ 148-150° / 80Pa)

[0169] Yield = 52%

[0170] CG analysis (surface) > 96%

[0171] The details of the CG analysis are given below. Compound CG (surface) 58,68% 26,91 % 7,82% 2,26% 0,37% Diester(s) 3,26% Example 1.8 - Préparation de Isoamyl-OOC-A MG -CONEt 2 (unclaimed)

[0172]

[0173] A crude mixture called "MGN" is hydrolyzed, consisting mainly of 2-methylglutaroinitrile (2-MGN), ethylsuccinonitrile (ESN), and adiponitrile (ADN), to obtain a mixture called MGA : Mixture comprising 2-methylglutaric acid (86% by moles), ethyl succinic acid (11% by moles) and adipic acid (3% by moles)

[0174] We carry out a transformation into anhydride according to procedure F.

[0175] The following steps are then carried out: Step 1 Raw materials

[0176] Cyclic anhydride DEA aq. 420 g; 3.28 mol; 1 Eq 880mL;8.53mol; 2.6.eq. Mw: 128.13; GC (surface) >99% Mw: 73.1

[0177] The acid amide is obtained according to procedure D.

[0178] Gross product = 765g (yellow liquid), >90% by CG Step 2 Raw materials

[0179] Acid amide 3-methylbutan-1-ol Thionyl chloride 660g; 3.3mol; 1Eq 364 g; 1.25 mol Eq 426 g; 3.6 mol; 1.1 eq Mw: 173.21 Mw: 88.15 Mw: 118.97; 99%

[0180] The diethyl amide ester is obtained according to Procedure E except that the acid amide is dissolved in dichloromethane before the reaction.

[0181] Final product = 460g (Boiling point ~ 150-158°C / 200Pa), Yield = 64%, GC analysis (surface) > 98%

[0182] The details of the CG analysis are given below. Compound CG (surface) 70,25% 16,07% 8,49% 4,45% 0,33% Diamide 0,41% Di-ester isomer ND Total surface area CG% 100% Example 1.9 - Preparation of Cyclohexyl-OOC-A MG -CONEt 2

[0183]

[0184] A crude mixture called "MGN" is hydrolyzed, consisting mainly of 2-methylglutaroinitrile (2-MGN), ethylsuccinonitrile (ESN), and adiponitrile (ADN), to obtain a mixture called MGA : Mixture comprising 2-methylglutaric acid (86% by moles), ethyl succinic acid (11% by moles) and adipic acid (3% by moles)

[0185] We carry out a transformation into anhydride according to procedure F.

[0186] Next, procedure D is carried out.

[0187] The following steps are then carried out: Raw materials

[0188] Acid amide Cyclohexanol Thionyl chloride 402 g; 2.0 mol; 1 Eq 240g; 2.4mol; 1.2Eq 160 mL; 2.2 mol; 1.1 eq Mw: 173.21 Mw: 100 Mw: 118.97; 99%

[0189] The diethyl amide ester is obtained according to Procedure E except that the acid amide is dissolved in dichloromethane before the reaction.

[0190] Final product = 418g (Boiling point ~ 142-146°C / 80Pa), Yield = 73.7%, GC analysis (surface) > 98%

[0191] The details of the CG analysis are given below. Compound CG (surface) Miscellaneous 0,53% Diester(s) 0,04% 70,65% 17,22% 7,03% 3,52% 0,74% Diamides 0,26% Total surface area CG% 100% Example 1.10 - Preparation of n-butyl-OOC-A MG-CONEt 2

[0192]

[0193] A crude mixture called "MGN" is hydrolyzed, consisting mainly of 2-methylglutaroinitrile (2-MGN), ethylsuccinonitrile (ESN), and adiponitrile (ADN), to obtain a mixture called MGA: Mixture comprising 2-methylglutaric acid (86% by moles), ethyl succinic acid (11% by moles) and adipic acid (3% by moles)

[0194] We carry out a transformation into anhydride according to procedure F.

[0195] Next, procedure D is carried out.

[0196] The following steps are then carried out: Raw materials

[0197] Acid amide n-butanol Thionyl chloride 500g, 2.335mol, 1Eq 270 mL, 2.92 mol, 1.25 Eq 187 mL, 2.57 mol, 1.1 eq Mw: 173.21 Mw: 74 Mw: 118.97, 99%

[0198] The diethyl amide ester is obtained according to Procedure E except that the acid amide is dissolved in dichloromethane before the reaction.

[0199] Final product = 443g (Boiling point ~ 144°C / 80Pa), % Yield = 72.8%, GC analysis (surface) > 98%

[0200] The details of the CG analysis are given below. Compound CG (surface) Miscellaneous 0,22% Diester(s) 0,36% 71,07% 17,98% 6,88% 2,61% 0,76% Diamide(s) 0,12% Total GC area% 100% Example 1.11 - Preparation of a mixture comprising - MeOOC-A MG -CONMe 2 (main compound) and MeOOC-A ES -CONMe 2

[0201] The formula of the main compound is Raw materials

[0202] Methanol Dimethylamine Sodium methylate in methanol Methyl diesters Sulfuric acid 800 kg 1300 kg 240 kg (60 kg MeONa) 4080 kg 55 kg 28.89 Kmol 1.11 Kmol 23.45 Kmol 0.55 Kmol

[0203] A transamidification reaction is carried out on a mixture of methyl diesters, comprising dimethyl 2-methylglutarate (85% by weight), ethylsuccinate (12% by weight) and adipate (3% by weight).

[0204] To a mixture of anhydrous methanol and dimethylamine gas cooled to 5 + / - 5°C, sodium methylate in methanolic solution is added, followed slowly, over 4 hours, by a mixture of methyl diesters while maintaining the temperature at 10 + / - 5°C. The reaction is completed in 8 hours at 15 + / - 5°C.

[0205] The excess dimethylamine is then removed by distillation to a temperature of 25 ± 5°C and a vacuum of 200 mb, carrying methanol with it. The condensed mixture of dimethylamine in methanol solution is recycled into the next feed.

[0206] The catalytic sodium methoxide is neutralized by concentrated sulfuric acid or by ion-exchange resins (sulfonic resins of the Amberlist or Amberlit type). The sodium sulfate or resin is removed from the medium by filtration and rinsed with fresh methanol.

[0207] The methanol is then removed by vacuum distillation (up to 120°C and 10 mb) carrying away the unreacted methyl diesters (representing 1% yield); the mixture of methanol and methyl diesters is recycled in the production of methyl diesters.

[0208] The product is then distilled at a maximum temperature of 140°C in the boiler and a vacuum of 5 mb; 4050 kg are recovered, representing a yield of 92.3%

[0209] The distillation residue still contains 280 kg of product (yield of 6.3%); it is recycled in the distillation of the next operation.

[0210] The typical analysis of the distilled product is as follows: Appearance : clear, colourless to light yellow liquid. Hair coloring: 100 APHA max CG Analysis: Sum of ester-amide isomers: 96% min Sum of diamide isomers: 3 + / - 1% Total number of unreacted diester isomers: 0.5% max Methanol: 500 ppm max Water content: 100 ppm max Acid value: 0.8 mg KOH / g of product max Example 1.12 - Preparation of t-butyl-OOC-A MG-CONMe 2 (unclaimed)

[0211]

[0212] The synthesis route is as follows (only the major species are represented):

[0213] A crude mixture called "MGN" is hydrolyzed, consisting mainly of 2-methylglutaroinitrile (2-MGN), ethylsuccinonitrile (ESN), and adiponitrile (ADN), to obtain a mixture called MGA: Mixture comprising 2-methylglutaric acid (86% by moles), ethyl succinic acid (11% by moles) and adipic acid (3% by moles)

[0214] We carry out a transformation into anhydride according to procedure F.

[0215] The following steps are then carried out: Step 1 Raw materials

[0216] Cyclic anhydride DMA aq. 370g; 2.89mol; 1eq. MW: 128.13; GC (surface) >99% 1152 ml; 7.51 mol; 2.6 eq. Mw: 45.08; 33% in water

[0217] The acid amide is obtained according to procedure D.

[0218] Raw product = 550g (pale yellow liquid) Step 2 Raw materials

[0219] amide-acid Dichloromethane Thionyl chloride 592 g; 3.42 mol; 1 Eq Mw: 173.21 1000mL 274ml; 3.76mol; 1.1eq; MW: 118.97; 99%

[0220] The amide acid is mixed with dichloromethane and then cooled to approximately 4°C. Thionyl chloride is slowly added over approximately 1.5 hours while maintaining a temperature below 25°C. The reaction mixture is stirred at room temperature for 10 hours. Volatile species are removed to obtain the crude product.

[0221] Gross product = 687g (dark liquid). Step 3 Raw materials

[0222] Gross product Step 2 Dichloromethane Tert-butanol 305g; 1.52mol; 1Eq Mw: 191.66 300mL + 300mL 72ml; 0.77mol; 2eq; MW: 74; 99%

[0223] Dichloromethane is mixed with tert-butanol and cooled to 4°C. The crude product from step 2, diluted in dichloromethane, is then slowly added over approximately 1.5 hours while maintaining a temperature below 10°C. Volatile compounds are removed using a rotary evaporator. The crude reaction product is treated with 1500 g of sodium bicarbonate and then filtered. The cake is washed with 1500 mL of dichloromethane, and the filtrate is dried over sodium sulfate. After evaporation of the solvent, the crude product is obtained. This is purified by distillation (120°C / 250 Pa).

[0224] Gross product = 301g

[0225] Final product = 150g

[0226] CG analysis (surface) > 98% (isomers 8 / 92) Example 1.13 - Preparation of Et-butyl-OOC-A MG-CONMe 2 (unclaimed)

[0227]

[0228] The synthesis route is as follows (only the major species are represented):

[0229] A crude mixture called "MGN" is hydrolyzed, consisting mainly of 2-methylglutaroinitrile (2-MGN), ethylsuccinonitrile (ESN), and adiponitrile (ADN), to obtain a mixture called MGA : Mixture comprising 2-methylglutaric acid (86% by moles), ethyl succinic acid (11% by moles) and adipic acid (3% by moles)

[0230] We carry out a transformation into anhydride according to procedure F.

[0231] The following steps are then carried out: Step 1 Raw materials

[0232] Cyclic anhydride DMA aq. 397g; 3.1mol; 1eq. MW: 128.13; GC (surface) >99% 1237 ml; 8.06 mol; 2.6 eq. Mw: 45.08; 33% in water

[0233] The acid amide is obtained according to procedure D.

[0234] Gross product = 599g (pale yellow liquid) Step 2 Raw materials

[0235] amide-acid 2-ethyl butanol dichloromethane Thionyl chloride 599g; 3.46mol; 1Eq Mw: 173.21 721g; 6.92 mol; Mw: 32.04 550mL 253ml; 3.49mol; 1.01eq; MW: 118.97; 99%

[0236] Methyl ester dimethyl amide is obtained according to Procedure E.

[0237] Gross product = 772g

[0238] Final product = 420g, Yield = 51.5%

[0239] CG analysis (surface) > 98% (isomers 8 / 92) Examples 2.1 and following - Uses as solvents - Plant protection formulations

[0240] By mixing the ingredients, formulations of various plant protection products are prepared, of the emulsifiable concentrate (EC) type.

[0241] The formulations include: the active ingredient, in quantity by weight (of active material) indicated in the table below, 10% by weight of Alkamuls ®< RC surfactant, marketed by Rhodia and, as solvent, the remainder of compound or material composition of the examples.

[0242] Example 2.1.1 is a comparative example where the product Rhodiasolv ®< ADMA10, Rhodia (Asia Pacific area): Alkyldimethylamide solvent is used as a solvent.

[0243] The following tests are performed: Visual observation at 25°C - The appearance of the formulation is noted, and the presence of crystals is noted. Visual observation at 0°C - The formulation is placed at 0°C for 7 days, and its appearance is noted, and the presence of crystals is noted (CIPAC MT39 test). Visual observation at 0°C with nucleation: A crystal of the active ingredient is introduced into the formulation that has been at 0°C for 7 days for nucleation, and the formulation is placed at 0°C again for 7 days. The appearance of the formulation is noted, and the presence of crystals is noted. Example Solvent Active Appearance at 25°C Appearance at 0°C Appearance at 0°C with nucleation 2.1.1C Rhodiasolv®< ADMA 10 Oxyfluorfen - 22% Crystal clear Crystal clear Crystals 2.1.2C Rhodiasolv®< ADMA 10 Propuxur - 20% Crystal clear Crystal clear Crystals 2.1.3C Rhodiasolv®< ADMA 10 Dimethoate - 40% Disorder Disorder Crystals 2.1.4C Rhodiasolv®< ADMA 10 Alachlor - 48% Crystal clear Crystals Crystals 2.1.10C Rhodiasolv®< ADMA 10 Difenconazole - 25% Crystal clear Crystal clear Crystal clear 2.1.11C Rhodiasolv®< ADMA 10 Triadimenol - 23% Crystal clear Crystal clear Crystals 2.2.2 Example 1.1 Propuxur - 20% Crystal clear Crystal clear Crystal clear 2.2.3 Example 1.1 Dimethoate - 40% Crystal clear Crystal clear Crystal clear 2.2.4 Example 1.1 Alachlor - 48% Crystal clear Crystal clear Crystals 2.2.6 Example 1.1 Fastac - 10% Crystal clear Crystal clear Crystal clear 2.2.7 Example 1.1 Phenmedipham - 16% Crystal clear Crystal clear Crystal clear 2.2.8 Example 1.1 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.2.9 Example 1.1 Tebuconazole - 25% Crystal clear Crystal clear Crystal clear 2.2.10 Example 1.1 Difenconazole - 25% Crystal clear Crystal clear Crystal clear 2.3.2 Example 1.2 Propuxur - 20% Crystal clear Crystal clear Crystal clear 2.3.3 Example 1.2 Propuxur - 20% Crystal clear Crystal clear Crystal clear 2.3.5 Example 1.2 Chlorpyrifos - 40% Crystal clear Crystal clear Crystal clear 2.3.6 Example 1.2 Fastac - 10% Crystal clear Crystal clear Crystal clear 2.3.7 Example 1.2 Phenmedipham - 16% Crystal clear Crystal clear Crystal clear 2.3.9 Example 1.2 Tebuconazole - 25% Crystal clear Crystal clear Crystal clear 2.3.10 Example 1.2 Difenconazole - 25% Crystal clear Crystal clear Crystal clear 2.4.1 Example 1.3 Oxyfluorfen - 22% Crystal clear Crystal clear Crystal clear 2.4.2 Example 1.3 Propuxur - 20% Crystal clear Crystal clear Crystal clear 2.4.4 Example 1.3 Alachlor - 48% Crystal clear Crystal clear Crystals 2.4.5 Example 1.3 Chlorpyrifos - 40% Crystal clear Crystal clear Crystal clear 2.4.6 Example 1.3 Fastac - 10% Crystal clear Crystal clear Crystal clear 2.4.7 Example 1.3 Phenmedipham - 16% Crystal clear Crystal clear Crystal clear 2.4.8 Example 1.3 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.4.9 Example 1.3 Tebuconazole - 25% Crystal clear Crystal clear Crystal clear 2.5.4 Example 1.5 Alachlor - 48% Crystal clear Crystal clear Crystals 2.5.5 Example 1.5 Chlorpyrifos - 40% Crystal clear Crystal clear Crystal clear 2.5.6 Example 1.5 Fastac - 10% Crystal clear Crystal clear Crystal clear 2.5.7 Example 1.5 Phenmedipham - 16% Crystal clear Crystal clear Crystal clear 2.5.8 Example 1.5 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.5.9 Example 1.5 Tebuconazole - 25% Crystal clear Crystal clear Crystal clear 2.6.4 Example 1.6 Alachlor - 48% Crystal clear Crystal clear Crystals 2.6.8 Example 1.6 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.6.11 Example 1.6 Triadimenol - 23% Crystal clear Crystal clear Crystal clear 2.7.4 Example 1.7 Alachlor - 48% Crystal clear Crystal clear Crystals 2.7.8 Example 1.7 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.8.4 Example 1.8 Alachlor - 48% Crystal clear Crystal clear Crystals 2.8.8 Example 1.8 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.9.4 Example 1.9 Alachlor - 48% Crystal clear Crystal clear Crystals 2.9.8 Example 1.9 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.9.9 Example 1.9 Tebuconazole - 25% Crystal clear Crystal clear Crystal clear 2.10.4 Example 1.10 Alachlor - 48% Crystal clear Crystal clear Crystals 2.10.8 Example 1.10 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.10.10 Example 1.10 Difenconazole - 25% Crystal clear Crystal clear Crystal clear 2.11.1 Example 1.11 Oxyfluorfen - 22% Crystal clear Crystal clear Crystal clear 2.11.3 Example 1.11 Dimethoate - 40% Crystal clear Crystal clear Crystals 2.11.4 Example 1.11 Propuxur - 20% Crystal clear Crystal clear Crystal clear 2.11.5 Example 1.11 Chlorpyrifos - 40% Crystal clear Crystal clear Crystal clear 2.11.7 Example 1.11 Phenmedipham - 16% Crystal clear Crystal clear Crystal clear 2.11.8 Example 1.11 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.11.9 Example 1.11 Tebuconazole - 25% Crystal clear Crystal clear Crystal clear 2.11.10 Example 1.11 Difenconazole - 25% Crystal clear Crystal clear Crystal clear 2.12.4 Example 1.12 Alachlor - 48% Crystal clear Crystal clear Crystals 2.12.5 Example 1.12 Chlorpyrifos - 40% Crystal clear Crystal clear Crystal clear 2.12.7 Example 1.12 Phenmedipham - 16% Crystal clear Crystal clear Crystal clear 2.12.8 Example 1.12 Propanil - 36% Crystal clear Crystal clear Crystal clear 2.12.9 Example 1.12 Tebuconazole - 25% Crystal clear Crystal clear Crystal clear 2.12.11 Example 1.12 Triadimenol - 23% Crystal clear Crystal clear Crystals 2.13.3 Example 1.13 Dimethoate - 40% Crystal clear Crystal clear Crystals 2.13.4 Example 1.13 Alachlor - 48% Crystal clear Crystal clear Crystals

Claims

1. Concentrated phytosanitary formulation comprising an active phytosanitary product and, as a solvent, an esteramide compound chosen from the following compounds, and their mixtures: - MeOOC-AMG-CONMe2 - MeOOC-AES-CONMe2 - PeOOC-AMG-CONMe2 - PeOOC-AES-CONMe2 - CycloOOC-AMG-CONMe2 - CycloOOC-AES-CONMe2 - EhOOC-AMG-CONMe2 - EhOOC-AES-CONMe2 - PeOOC-AMG-CONEt2 - PeOOC-AES-CONEt2 - CycloOOC-AMG-CONEt2 - CycloOOC-AES-CONEt2 - BuOOC-AMG-CONEt2 - BUOOC-AES-CONEt2 where - AMG represents an MGa group of formula -CH(CH3)-CH2-CH2-, or MGb group of formula - CH2-CH2-CH(CH3)- or a mixture of MGa and MGb groups; - AES represents an ESa group of formula -CH(C2H5)-CH2-, or ESb group of formula - CH2-CH(C2H5)- or a mixture of ESa and ESb groups; - Pe represents a pentyl group; - Cyclo represents a cyclohexyl group; - Eh represents a 2-ethylhexyl group; and - Bu represents a butyl group.

2. Concentrated phytosanitary formulation according to claim 1, characterized in that the esteramide has a melting point that is less than or equal to 20°C.

3. Concentrated phytosanitary formulation according to any one of the preceding claims, wherein the active phytosanitary product is solid and insoluble in water.

4. Concentrated phytosanitary formulation according to any one of the preceding claims, wherein the active phytosanitary product is a herbicide, an insecticide, an acaricide, a fungicide or a rodenticide.

5. Concentrated phytosanitary formulation according to any one of the preceding claims, wherein the active phytosanitary product is chosen from the group consisting of: Alachlor, Chlorpyrifos, alpha-cypermethrin, Phenmedipham, Propanil, Pendimethalin, triadimenol, Trifluralin, Oxyfluorfen, Dimethoate, Imidacloprid, Proxopur, Benomyl, Deltamethrine, Fenvalerate, Abamectin, Amicarbazone, Bifenthrin, Carbosulfan, Cyfluthrin, Difenconazole, Ethofenprox, Fenoxaprop-ethyl, Fipronil, Fenvalerate, Fluazifop-p-butyl, Flufenouron, Hexazinone, Lambda-cyalothrin, Methomyl, Permethrin, Prochloraz, Propiconazole and Tebuconazole.

6. Concentrated phytosanitary formulation according to any one of the preceding claims, further comprising an emulsifier.

7. Concentrated phytosanitary formulation according to any one of the preceding claims, wherein the water content is less than 50% by weight.

8. Concentrated phytosanitary formulation according to any one of the preceding claims, comprising: a) from 4 to 60% of the phytosanitary product, by weight of active ingredient; b) from 10 to 92% of solvent, by weight; c) from 4 to 60% by weight of solids, of an emulsifier; and d) from 0 to 10% by weight of water.