Classifications

• • 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
  • C07D211/80—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 two double bonds between ring members or between ring members and non-ring members
  • C07D211/84—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 two double bonds between ring members or between ring members and non-ring members 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
  • C07D211/86—Oxygen atoms
  • C07D211/88—Oxygen atoms attached in positions 2 and 6, e.g. glutarimide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
  • C07C67/20—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from amides or lactams
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/36—Oxygen or sulfur atoms
  • C07D207/40—2,5-Pyrrolidine-diones
  • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere

Definitions

• the subject of the present invention is a process for the preparation of imides and the uses thereof, especially as intermediates for the preparation of solvents, in particular diester solvents.
• the invention relates to a process for the preparation of cyclic imides and their derivatives, especially the corresponding carboxylic acid diesters.
• Diesters are a category of oxygenated solvents that are interesting because of their technical performance and low environmental impact. They have replaced hydrocarbon solvents, chlorinated or oxygenated, more aggressive for the environment, in a large number of industrial applications such as degreasing, paint stripping ...
• a first preparation method for example described in WO2007 / 141404, is a reaction between a dinitrile and a basic compound, in a solvent, followed by acidification with a mineral acid to recover the corresponding dicarboxylic acid which can then be esterified to using an alcohol.
• the disadvantage of this process is that it generates salts, for example, ammonium or sodium, as co-products.
• a third method of preparation is described in particular in WO2009 / 056477. It differs from the process described in WO2008 / 009792 by its second step in which the reaction between the imide and the alcohol can be carried out in basic catalysis or without catalyst.
• the first step of synthesizing the imide of the two processes above has the drawback of forming ammonia, which is then to be recovered and treated.
• the need lies in a rationalization and optimization of industrial tools.
• One of the aims of the present invention is therefore to propose a method for manufacturing intermediates in the preparation of solvents, in particular diesters, from compounds of fossil origin to be efficientlyzed and / or bio-sourced that do not have the drawbacks of processes of the prior art and in particular not generating significant effluents or by-products and possibly harmful to the environment.
• the invention meets this need by proposing a process for the preparation of cyclic imide (s) by reaction between at least one dicarboxylic acid and at least one dinitrile. More specifically, the invention relates to a process for the preparation of cyclic imide (s) of
• a 1 and A 2 are the same or different and are selected from the following divalent hydrocarbon groups:
• alkylene comprising a linear sequence having 2 or 3 carbon atoms; ortho-cycloalkylene having 5 or 6 carbon atoms; alkenylene comprising a linear sequence having 2 or 3 carbon atoms;
• one or more hydrogen atoms of said hydrocarbon groups may be substituted by a group R, R being selected from the following substituents: C1-C10 alkyl, C5-C6 cycloalkyl, C6-C10 aryl, C6-C10 alkylaryl, C 6 -C 10 arylalkyl, hydroxy or halo; one or more hydrogen atoms of the alkylene and cycloalkylene groups may also be substituted by a group R ', R' being a C1-C10 alkylidene.
• R is a C 1 -C 10 alkyl group, it is preferably chosen from linear or branched alkyls having from 1 to 4 carbon atoms.
• R is a methyl or an ethyl.
• R is a C5-C6 cycloalkyl group, it is selected from cyclopentyl and cyclohexyl.
• R is a C 6 -C 10 aryl group, it is preferably a phenyl or a naphthyl.
• R is a C 6 -C 10 alkylaryl group, it is preferably a benzyl.
• R is a C 6 -C 10 arylalkyl group
• tolyl will preferably be selected.
• halo is meant fluorine, chlorine, bromine and iodine.
• alkylene By “hydroxy” is meant the -OH group.
• alkylene there may be mentioned ethylene or propylene, substituted or not by one or more, preferably only one, group R and / or R 'as defined above. Particularly preferably, the following alkylene groups will be selected: ethylene, propylene, ethyl-ethylene, 1-methylpropylene and mixtures thereof.
• ortho-cycloalkylene it is in particular ortho-cyclopentylene or ortho-cyclohexylene, substituted or not by one or more, preferably a single, group R such that previously defined.
• ortho-cycloalkylene groups will be selected: ortho-cyclopentylene, ortho-cyclohexylene and mixtures thereof.
• the following alkenylene groups will be selected:
• -CH CH-CH 2 -
• -CH CH-CH (CH 3 ) -
• -CH CH-CH (CH 2 CH 3 ) -
• -C (CH 3 ) CH-CH 2 -
• -CH C (CH 3 ) -CH 2 -
• ortho-arylene examples include orthophenylene optionally substituted with one or more, preferably only one group R as defined above and below in the description. Particularly preferably, ortho-phenylene, hydroxy-ortho-phenylene and mixtures thereof will be chosen.
• the present invention also relates to the use of cyclic imides of formulas (I) and (II) as defined above, as intermediates for the preparation of solvents.
• the present invention also provides a process for the preparation of diester (s) of carboxylic acid (s) which comprises:
• the process for the preparation of cyclic imide (s) according to the invention involves at least one dicarboxylic acid of formula (III).
• the dicarboxylic acid of formula (III) may be of biological origin according to ASTM D6866 or obtained by fermentation of sugars, molasses, glucose or starch.
• the dibasic carboxylic acid of biological origin according to the ASTM D6866 standard or obtained by fermentation of sugars, molasses, glucose or starch used in the process of the invention may be chosen from succinic acid, glutaric acid, lactic acid and the like. itaconic acid and citraconic acid.
• the dicarboxylic acid of formula (III) may be a by-product resulting from the adipic acid production reaction. It may be the adipic acid production reaction, by nitric oxidation of cyclohexanol or a cyclohexanol / cyclohexanone mixture. It may also be the adipic acid production reaction, by direct oxidation of cyclohexane by an oxygen-containing gas, for example oxygen from the air.
• the dicarboxylic acid of formula (III) being a by-product from the adipic acid production reaction is a mixture comprising predominantly glutaric acid and succinic acid.
• cyclic imide (s) is a mixture comprising more than 70% by weight of glutaric acid and succinic acid. This may especially be a mixture comprising from 40 to 95% by weight of glutaric acid, preferably from 45 to 85% by weight, and from 5 to 60% by weight of succinic acid, preferably from at 55% by weight. In addition, the mixture may comprise up to 20% by weight of adipic acid.
• a mixture of dicarboxylic acids can be used raw or be previously purified by removal of picric acid, nitric acid, metals and the water it contains. Such a purification treatment can be in particular a distillation (topping / tailing).
• the process for the preparation of cyclic imide (s) according to the invention also involves at least one dinitrile of formula (IV).
• the dinitrile of formula (IV) may be of biological origin according to ASTM D6866.
• it may be chosen from succinonitrile of biological origin, glutaronitrile of biological origin, itaconitrile of biological origin and citraconitrile of biological origin, all meeting the ASTM D6866 standard.
• the dinitrile of formula (IV) may be a by-product of the adiponitrile production reaction, by hydrocyanation of butadiene.
• the dinitrile of formula (IV) is a by-product of the adiponitrile production reaction by hydrocyanation of butadiene, it is preferably a mixture comprising predominantly 2-methylglutaronitrile and 2-ethylsuccinonitrile.
• “predominantly” it will be understood that it is a mixture comprising more than 80% by weight of 2-methylglutaronitrile and 2-ethylsuccinonitrile.
• This mixture comprises, for example, 70 to 95% by weight of 2-methylglutaronitrile, preferably 80 to 95% by weight, and 5 to 30% by weight of 2-ethylsuccinonitrile, preferably 5 to 20% by weight.
• Such a mixture of dinitriles can be used raw or be previously purified by removal of phosphorus, nitrile pentenes and hydroxylated aromatics it contains. Such a purification treatment may in particular be a topping or an adsorption.
• the reaction between at least one dicarboxylic acid of formula (III) and at least one dinitrile of formula (IV) takes place without a catalyst.
• the reaction between at least one dicarboxylic acid of formula (III) and at least one dinitrile of formula (IV) takes place in the presence of an acid catalyst.
• the acid catalyst may be organic or inorganic. It is usually a protic acid (Bronsted).
• the acid catalyst chosen will advantageously be an acid slightly corrosive vis-à-vis facilities with which it is in contact.
• the acid catalyst may be soluble in the reagent mixture, thus allowing homogeneous or insoluble catalysis in the reagent mixture, thus allowing heterogeneous catalysis.
• mixture of reagents is meant that it is the mixture of diacid (s) carboxylic (s) of formula (III) and dinitrile (s) of formula (IV) at the beginning of the reaction.
• the soluble acid catalyst in the reaction mixture it is carried out among orthophosphoric acid (H 3 PO 4 ), metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphonic acid, sulfuric acid, sulphonic acid and mixtures thereof. .
• Orthophosphoric acid (H 3 PO 4 ) is preferred.
• the acid catalyst is preferably used pure or in concentrated solution, that is to say in a concentration by weight greater than 75%, preferably greater than 80%. It may be an aqueous or organic solution, preferably an aqueous solution. As regards the catalyst that is insoluble in the reaction mixture, it may be sulphonic resins, preferably NAFION, zeolites, preferably HBEA, HY or HMOR zeolites, and clays, preferably montmorillonites or silicas. -alumines, or aluminas, preferably gamma or alpha-alumina.
• aluminas preferably gamma alumina, will be selected.
• This type of insoluble catalyst is generally used when the reaction is conducted continuously, the catalyst is then implemented in fixed bed or fluidized, preferably fixed bed.
• at least one polymerization inhibitor may be added to the reaction between the diacid (s) carboxylic acid (s) ( s) of formula (s) (III) and the dinitrile (s) of formula (s) (IV).
• the polymerization inhibitor is advantageously chosen from diphenols, preferably hydroquinone or 4-tert-butyl catechol and phenothiazines, preferably 8-hydroxyphenothiazine.
• the cyclic imide (s) preparation reaction according to the process of the invention is a stoichiometric reaction involving one mole of dicarboxylic acid of formula (III) for one mole of dinitrile of formula (IV).
• the molar ratio between the dinitrile of formula (IV) and the dicarboxylic acid of formula (III) is advantageously between 1 and 1, 2 inclusive. This slight molar excess of dinitrile of formula (IV) may be necessary to compensate the dinitrile losses due to the evaporation of said dinitrile during the reaction.
• the dicarboxylic acid and the dinitrile can be reacted in the presence of an acid catalyst.
• the amount of catalyst that is used in the process of the invention can vary within wide limits.
• the amount of homogeneous acidic catalyst represents at most 1% by weight, preferably between 0.01 and 1% by weight, relative to the weight of the reaction mixture at the beginning of the reaction.
• the temperature at which the cyclic imide preparation reaction of formulas (I) and (II) is carried out depends on the reactivity of the reactants, their physical properties and the presence or absence of acid catalyst in the reaction mixture.
• the reaction is carried out at the reflux temperature of the dinitrile of formula (IV). Generally, this temperature is between 200 ° and 300 ° C, preferably between 240 ° C and 280 ° C.
• the reaction is conducted at atmospheric pressure but lower or higher pressures may also be suitable. It is operated under autogenous pressure when the reaction temperature is higher than the boiling point of the reagents and / or products.
• the process of the invention is carried out under a controlled atmosphere of inert gases. It is possible to establish an atmosphere of rare gases, preferably argon, but it is more economical to use nitrogen.
• the reaction according to the process of the invention is generally in bulk, that is to say that the reagents are not diluted in a solvent.
• the invention does not exclude the use of a solvent, such as, for example, sulfolane or isopar. From a practical point of view, the process can be carried out batchwise or continuously.
• the order of implementation of the reagents for the preparation of the imides is not critical.
• the dinitrile of formula (IV) and then the dicarboxylic acid of formula (III) and, where appropriate, the soluble acid catalyst are charged to a stirred reactor.
• the reaction mixture is stirred at the desired temperature. It is left stirring until complete consumption of the reagents which can be followed by analytical method, for example gas chromatography.
• the size of the catalytic bed is adapted to the flow rate of the two reagents so as to obtain a complete conversion of the reagent in default at the outlet of the catalytic bed.
• a liquid phase comprising the imides of formulas (I) and (I) is recovered.
• the imides of formulas (I) and (I) can then crystallize on return to ambient temperature.
• This liquid phase at the temperature of the reaction, or the crystals after return to ambient temperature can be reused directly in another process without purification operation.
• These can also be slightly treated by means of tarring / etching operation (s).
• Thawing is generally an operation that aims to remove the heavier products resulting from the degradation of the reagents and products of the reaction.
• Topping is usually an operation that aims to eliminate excess dinitrile.
• the catalyst it is also possible at the end of the reaction to separate the catalyst. If it is insoluble, it can be separated by a solid / liquid separation technique preferably by filtration. If the catalyst is soluble, such as, for example, phosphoric acid, it is neutralized with a base such as sodium hydroxide and is then subjected to distillation, the neutralized catalyst then being recovered at the bottom of the column.
• a base such as sodium hydroxide
• the imides of the following formulas are preferred:
• cyclic imide mixtures comprising:
• the method according to the invention described above makes it possible to obtain a dinitrile conversion rate close to 100% and imide yields greater than 90%, preferably greater than 95%.
• the method of the invention is particularly interesting because it generates no by-products and allows total atom saving, ie the process does not generate nitrogen oxide, carbon dioxide, or ammonia, water or salt and that 100% of the atoms introduced at the beginning of the reaction are found in the product obtained. It is also simple to implement in industrial facilities and economically efficient because productive. It is also respectful of the environment since no toxic or harmful product is produced.
• the method of the invention also allows the use of bio-sourced reagents, which is particularly advantageous from an industrial point of view given the depletion of fossil resources.
• the process of the invention allows the upgrading of industrial waste, hitherto burned, noble products used without heavy purification treatment, which represents a significant ecological and economic gain.
• the process of the invention also has the advantage of producing directly transformable imides without additional purification steps, which are generally time consuming and energy consuming.
• the present invention also relates to the use of imides of formulas (I) and (II), in particular obtained by the method previously described, as intermediates for the preparation of solvents.
• Such solvents may in particular be carboxylic acid diesters.
• the imides of formulas (I) and (II), in particular obtained by the process for the preparation of cyclic imide (s) of formulas (I) and (II) of The invention can be engaged in a deaerating alcoholysis reaction and lead to the corresponding carboxylic acid diesters.
• the present invention also provides a process for the preparation of diester (s) of carboxylic acid (s) which comprises:
• the first step is the preparation of cyclic imide (s) of formulas (I) and ( II) according to the process for the preparation of cyclic imide (s) of formulas (I) and (II) above in the description.
• R represents a hydrocarbon group comprising from 1 to 20 atoms.
• the group R may be aliphatic, cycloaliphatic, aromatic or arylalkyl,
• the group R may also include heteroatoms or substituents.
• heteroatom is meant by way of example and without being limited thereto, the following atoms: O, N, S, P.
• substituteduents we mean by way of example and without, however, 'to limit the following atoms: Cl, Br, I, F.
• the alcohol of formula (V) used in this second step of the process for the preparation of diester (s) of carboxylic acid (s) according to the invention is chosen from the following alcohols: methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, hexanol, cyclohexanol, 2-ethylhexanol, isooctanol, benzyl alcohol and mixtures thereof.
• the reaction between the imides of formulas (I) and (II) and at least one alcohol takes place in the presence of a catalyst.
• the catalyst may be an acidic or basic catalyst, preferably an acid catalyst.
• acid catalyst is meant an acid catalyst in the Lewis sense, as defined in the literature, in particular by Jerry MARCH, Advanced Organic Chemistry, 3rd edition, John Wiley and Sons, 1985, pp. 227 and following, or a catalyst identified as such in the present application.
• the acid catalyst may be soluble in the starting reaction mixture, thus allowing homogeneous or insoluble catalysis in the starting reaction mixture, thus allowing heterogeneous catalysis.
• homogeneous catalysis is carried out using a soluble catalyst in the starting reaction mixture.
• starting reaction mixture is meant for this deaerating alcoholysis reaction, that it is the mixture of imide (s) of formula (I) and (II) and alcohol (s) at the beginning of the reaction.
• the soluble acid catalyst in the starting reaction mixture may be a lanthanide salt, for example a triflate, a chloride or a nitrate.
• the soluble acid catalyst is preferably used pure or in concentrated solution, that is to say in a concentration by weight greater than 75%, preferably greater than 80%. It may be an alcoholic solution, preferably a methanolic solution.
• the acid catalyst insoluble in the starting reaction mixture may be a solid acid catalyst, typically used in a heterogeneous phase, for example chosen from:
• metal oxides such as alumina, titanium oxides, silica / alumina mixtures and the like,
• acid phosphates such as NaH 2 PO 4 or silicon orthophosphate.
• basic catalyst is meant a basic Lewis catalyst, as defined in the literature, in particular by Jerry MARCH, Advanced Organic Chemistry, 3rd edition, John Wiley and Sons, 1985, pp. 227 and following, or a catalyst identified as such in the present application.
• the basic catalyst may be soluble in the starting reaction mixture, thus allowing homogeneous or insoluble catalysis in the starting reaction mixture, thus allowing heterogeneous catalysis.
• starting reaction mixture is meant for this deaerating alcoholysis reaction, that it is the mixture of imide (s) of formula (I) and (II) and alcohol (s) at the beginning of the reaction.
• soluble basic catalyst an organic salt comprising a basic anion.
• alkali or alkaline earth salts of compounds comprising a sulfate, sulfonate, phosphate or phosphonate group or organic compounds comprising a carboxylate or alkoxide group (or "alkylate”).
• potassium, sodium or lithium alcoholates especially sodium ethanolate or lithium ethanolate.
• a mineral base it is possible to use, as soluble basic catalyst, a mineral base. It may be a nitrogenous or non-nitrogenous mineral base.
• water-soluble alkaline salts such as hydroxides, inorganic carbonates and inorganic phosphates.
• bases there may be mentioned hydroxides such as NaOH, KOH, LiOH and strong base salts with a weak acid such as K 2 CO 3 and Na 2 CO 3 , K 3 PO 4 , Li 3 PO 4 .
• an alkali metal in metallic form for example sodium, is used as the soluble catalyst.
• the base used may be a heterogeneous catalyst based on hydroxides and / or oxides of alkali, alkaline earth and / or lanthanide. It may especially be magnesia (MgO), Mg (OH) 2 , CaO, Ca (OH) 2 , BaO, Ba (OH) 2 , La 2 O 3 .
• It may be in particular a catalyst chosen from oxides, hydroxides and basic salts of alkaline earth and / or rare earths having no degree of valence IV and among the minerals containing it.
• hydrotalcite a natural minerals or synthetic analogues which consist of intercalated layers based on oxides or metal hydroxides, such as hydrotalcite. It may in particular be a natural hydrotalcite or a synthetic analogue.
• These basic salts may contain various combinations of M 2+ metal cations such as Mg 2+ , Zn 2+ , Cu 2+ Ni 2+ , Te 2+ , Co 2+ and trivalent cations. of type M as Al, Cr, Fe.
• the anions associated with these metal cations may be halogens, organic anions or oxanions.
• hydrotalcites there may be mentioned in particular that which corresponds to the formula [Mg 6 A, 2 (O 4 ) 16 ] CO 3 .4H 2 O.
• rare earth oxides and carbonates can be used, such as ytterbium and lanthanum.
• alkali metal alkoxides especially sodium methoxide, sodium ethoxide, sodium tert-butylate, potassium methoxide, potassium ethoxide, potassium tert-butoxide, preferably sodium methoxide,
• the second step of the preparation of diester (s) carboxylic acid (s) according to the process of the invention is a reaction involving two moles of alcohol per mole of imide.
• the reaction step between a dicarboxylic acid of formula (III) and a dinitrile of formula (IV) leads to the formation of two moles of cyclic imide (s) of formulas (I) and (II).
• the molar ratio between the alcohol and the mixture of cyclic imides of formulas (I) and (II) is advantageously between 4 and 20 inclusive.
• the amount of catalyst used in the preparation of diester (s) carboxylic acid (s) according to the process of the invention is preferably less than 25% by weight, preferably less than 10% by weight, and even more preferably between 1 and 5% by weight, relative to the weight of imide (s) cyclic (s) of formulas (I) and (II).
• the temperature at which the deaerating alcoholysis reaction is carried out depends on the reactivity of the reactants and the presence or absence of catalyst in the starting reaction mixture.
• the deaerating alcoholysis reaction can be carried out in the liquid or vapor phase, preferably in the liquid phase.
• the deaerating alcoholysis reaction is conducted in the liquid phase at a temperature below 400 ° C., preferably between 100 and 300 ° C.
• the deaerating alcoholysis reaction is conducted at a pressure of 1 to 100 bar, preferably at autogenous pressure.
• reaction temperature is higher than the boiling point of the reagents and / or products.
• ammonia is formed, which is recovered during this step.
• the deaerating alcoholysis reaction according to the process of the invention is generally carried out in bulk, that is to say that the reagents are not diluted in a solvent, the reagents, and in particular the alcohol, participating in the reaction. homogeneity of the starting mixture. From a practical point of view, the process can be carried out batchwise or continuously.
• a liquid phase is recovered, generally after condensation of the gaseous phase, comprising the carboxylic acid diesters.
• the diesters contained in this phase can then be recovered by any conventional means known to those skilled in the art, in particular by distillation or extraction.
• the order of implementation of the reagents for the alcoholic hydrolysis reaction is not critical.
• the alcohol of formula (V) and then the imides of formulas (I) and (II) and, where appropriate, the catalyst are loaded in a stirred reactor operating for example continuously.
• reaction mixture After bringing the reactants into contact, the reaction mixture is stirred at the desired temperature.
• carboxylic acid diesters of the following formulas alone or as a mixture: R "
• R " is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, isopentyl, hexyl, cyclohexyl, 2-ethylhexyl, isooctyl, benzyl and mixtures thereof, for example mixtures of the oil
• R " is methyl, ethyl, propyl or mixtures thereof.
• diesters have various applications, especially as solvents in the field of painting, cleaning, stripping, and agrochemistry.
• diesters of the invention can be used as solvents or co-solvents
• the conversion ratio (TT) corresponds to the ratio between the number of moles of substrate transformed and the number of moles of substrate involved.
• the yield (RR) corresponds to the ratio between the number of moles of product formed and the number of moles of substrate engaged.
• EXAMPLE 5 Preparation of a mixture of imides from pure MGN and of bio-sourced succinic acid 23 g of 2-methyl-glutaronitrile are introduced into a 100 ml reactor and then 25 g of succinic acid are added. obtained by fermentation. 0.1 g of 85% orthophosphoric acid are stirred and added. The reaction medium is heated to 270 ° C. and maintained under these conditions for 2 hours. By GC analysis, we obtain the following results:
• 300 g of a mixture of imides obtained, for example in Example 4 are introduced into a 300 ml reactor. 90 g of methanol and 0.25 g of sodium methoxide are added. The reaction medium is heated with stirring under autogenous pressure and maintained for 6 hours under these conditions. After cooling, the reaction medium is analyzed by gas chromatography. For a conversion of 92% of the sum of the imides, a yield of a mixture of methyl diesters of 65% is obtained.

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