EP2729446A1 - Process for producing compounds comprising nitrile functions - Google Patents

Process for producing compounds comprising nitrile functions

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Publication number
EP2729446A1
EP2729446A1 EP12733683.2A EP12733683A EP2729446A1 EP 2729446 A1 EP2729446 A1 EP 2729446A1 EP 12733683 A EP12733683 A EP 12733683A EP 2729446 A1 EP2729446 A1 EP 2729446A1
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EP
European Patent Office
Prior art keywords
carbon atoms
acid
general formula
mixture
nitrile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP12733683.2A
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German (de)
French (fr)
Inventor
Philippe Marion
Roland Jacquot
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Rhodia Operations SAS
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Rhodia Operations SAS
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Publication of EP2729446A1 publication Critical patent/EP2729446A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/02—Preparation by ring-closure or hydrogenation
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no 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
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to the manufacture of compounds comprising nitrile functions and cyclic imide compounds.
  • nitrile functions from compounds comprising carboxylic functions, preferably of natural and renewable origin, and from an N mixture of dinitriles comprising 2-methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN) and adiponitrile (AdN).
  • MGN 2-methylglutaronitrile
  • ESN 2-ethylsuccinonitrile
  • AdN adiponitrile
  • amine compounds comprising nitrile functions are important products for the manufacture of amine compounds.
  • the dinitrile compounds lead to amines which are, for example, monomers which are the origin of polymers such as polyamide, for example.
  • the mononitrile compounds lead to amines or amides which are for example used for the manufacture of cationic surfactants.
  • nitrile synthesis processes including synthetic processes from ammonia and carboxylic acids. These processes mainly use hydrocarbon compounds derived from petroleum refining, and ammonia, which are obtained from hydrogen from steam reforming processes that consume gas and energy, as starting material.
  • renewable resources can be produced from plant material grown or not, such as trees, plants such as sugar cane, maize, cassava, wheat, rapeseed, sunflower, palm, castor oil or the like.
  • This plant material is transformed by methods generally comprising several mechanical, chemical and biological steps.
  • adiponitrile a large chemical intermediate used in particular in the synthesis of hexamethylene diamine and caprolactam (monomers for the manufacture of polyamides), obtained by hydrocyanation of butadiene, generates a stream of dinitrile byproducts comprising predominantly branched dinitrile compounds such as 2-methylglutaronitrile, 2-ethylsuccinonitrile.
  • This mixture of branched dinitrile compounds is obtained by distillation to separate it from adiponitrile. Since the separation is generally not complete, the mixture of branched dinitrile compounds may also comprise a small proportion of adiponitrile.
  • This process requires purification steps of 2-methylglutaronitrile and 2-methylpentamethylenediamine.
  • the invention provides a process for the preparation of at least one nitrile of general formula I
  • y 1 or 2
  • R represents a hydrogen atom or one or more substituents
  • an N mixture of dinitriles comprising 2-methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN) and adiponitrile (AdN) is used. At least the cyclic imides 3-methylglutarimide and 3-ethylsuccinimide are obtained.
  • MGN 2-methylglutaronitrile
  • ESN 2-ethylsuccinonitrile
  • AdN adiponitrile
  • the N mixture of dinitriles is a mixture resulting from the process for the manufacture of adiponitrile by double hydrocyanation of butadiene. It preferably corresponds to the distillation fraction making it possible to separate the branched dinitriles (2-methylglutaronitrile, 2-ethylsuccinonitrile) from adiponitrile.
  • This mixture of dinitriles generally has the following composition by weight:
  • 2-methylglutaronitrile between 70% and 95%, preferably between 80 and 85%
  • Adiponitrile between 0% and 10%, preferably between 1 and 5%, the 100% complement corresponding to different impurities
  • the process of the invention uses a carboxylic acid of general formula II as described above.
  • the carboxylic acid of general formula II or IV is derived from a renewable material of vegetable origin.
  • a material or renewable resource is a natural resource, animal or plant, whose stock can be reconstituted over a short period on a human scale. In particular, this stock must be renewed as quickly as it is consumed.
  • renewable raw materials contain a significant proportion of 14 C.
  • the nitriles of the invention consist of organic carbon from renewable raw materials.
  • this preferred characteristic could be certified by determination of the 14 C content according to one of the methods described in the ASTM D6866 standard, in particular according to the mass spectrometry method or the liquid scintillation spectrometry method which are described in this standard. .
  • renewable resources can be produced from plant material grown or not such as trees, plants such as sugar cane, corn, cassava, wheat, rapeseed, sunflower palm, castor or like.
  • the carboxylic acid of general formula II or IV may be derived from renewable resources such as natural polysaccharides such as starch or cellulose, the starch being able to be extracted, for example, from maize, wheat or potato. It can in particular come from various transformation processes, including conventional chemical processes, enzymatic transformation processes or by fermentation.
  • 2,5-Furannedicarboxylic acid can for example be obtained from mucic acid or from hydroxymethylfurfural.
  • R is chosen from:
  • linear or branched alkyl groups preferably having from 1 to 6 carbon atoms and even more preferentially from 1 to 4 carbon atoms,
  • linear or branched mono, poly or perhalogenated alkyl groups preferably having from 1 to 6 carbon atoms and from 1 to 13 halogen atoms and even more preferably from 1 to 4 carbon atoms and from 1 to 9 carbon atoms; halogen atoms,
  • R 2 represents a linear or branched alkyl group having from 1 to 6 carbon atoms and even more preferably from 1 to 4 carbon atoms or the phenyl group ,
  • halogen atom preferably a fluorine atom.
  • y is 1 and R represents -CO-O-R 3 with R 3 which represents an alkyl group having 1 to 4 carbon atoms in the general formula II or IV
  • the compound of formula II or IV is selected from 2,5-furannedicarboxylic acid, 2,5-tetrahydrofurannedicarboxylic acid, 2-furoic acid, 2,5-furannedicarboxylic acid monomethyl ester or 2,5-tetrahydrofuranyl dicarboxylic acid monomethyl ester.
  • the compound of formula IV when the compound of formula IV is 2,5-tetrahydrofurannedicarboxylic acid, it can be used in the form of the trans isomer, the cis isomer or a mixture of the isomer cis and trans isomer.
  • the process of the invention is advantageously carried out at a temperature of between 150 and 350 ° C.
  • the pressure used is generally between atmospheric pressure and a few bars.
  • Catalysts can be implemented in the context of the process of the invention.
  • catalysts mention may be made of phosphoric acid, phosphates, borophosphates, sulfuric acid, sulphonic acid, benzene sulphonic acid, toluene sulphonic acid, such as para toluene sulphonic acid, naphthalene sulfonic acids, silica, alumina, clay, silica / alumina.
  • a quantity of 2-methylglutaronitrile (MGN) or of mixture N is used such that at least one molecule of 2-methylglutaronitrile (MGN) or 2-ethylsuccinonitrile ( ESN) is introduced into the reaction medium, by acid function of the carboxylic acid of general formula II or IV to be converted into a nitrile function.
  • imides are formed, in particular 3-methylglutarimide from MGN and 3-ethylsuccinimide from the ESN.
  • the process of the invention also comprises a step of recovering at least the nitrile of formula (I) or (III) on the one hand, and at least the cyclic imide on the other hand from the reaction medium.
  • This recovery can be carried out by separation of the compounds of the reaction medium, according to any known method such as distillation.
  • the compounds can be obtained by reactive distillation.
  • the nitrile of formula (I) or (III) that it is desired to obtain has a boiling point lower than that of the reaction temperature (which is particularly the case for nitriles having a low number of carbons)
  • this nitrile can be distilled as it is formed, displacing the equilibrium of the reaction in favor of the formation of this nitrile; this is therefore particularly advantageous.
  • This reactive distillation method may for example be used when the nitrile of formula (I) or (III) is 2,5-dicyanotetrahydrofuran or a mononitrile.
  • the compounds can be separated by extraction with hot water.
  • the imides are generally soluble in water, unlike nitriles, which allows a good separation by an easy way to implement.
  • This route is preferred especially when the nitriles and imides to be separated have boiling temperatures that are close and they are therefore difficult to separate by conventional distillation, for example.
  • the temperature of the water during this extraction is generally greater than or equal to 50 ° C.
  • the nitrile of formula (I) or (III) thus recovered is hydrogenated to form the corresponding amine, according to a method known to those skilled in the art.
  • a nitrile of formula (I) is recovered, its hydrogenation can lead to the amine corresponding to the compound of formula (III), by hydrogenation not only of the nitrile function, but also by hydrogenation of the double bonds of the furan ring.
  • an amine in which all the carbons are biobased (because derived from a biosourced carboxylic acid, that is to say a carboxylic acid derived from a renewable raw material), and whose nitrogen atoms are recycled ( as derived from by-products usually burned which generates carbon dioxide and oxides of nitrogen, greenhouse gases that must be treated to meet the legislation in force).
  • the diamines can be used as raw materials for the manufacture of polyamides, which will thus be partially or completely biobased depending on the acids used for the polymerization.
  • Amines can also be used to prepare surfactants.
  • the cyclic imide recovered according to the process of the invention can be reacted with an alcohol to form the corresponding diester.
  • an alcohol such as WO2008 / 009792 and WO 2009/056477.
  • the diesters can be used as solvents.
  • THFDCA cis 2,5-tetrahydrofuran dicarboxylic acid
  • reaction medium is then analyzed by GPC and the following results are obtained:
  • reaction medium is then analyzed by GPC and the following results are obtained:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

The present invention relates to the production of compounds comprising nitrile functions and of cyclic imide compounds. It relates more particularly to the production of compounds comprising nitrile functions from compounds comprising carboxylic functions, advantageously of natural and renewable origin, and from 2-methylglutaronitrile (MGN) or a mixture N of dinitriles comprising 2-methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN) and adiponitrile (AdN).

Description

PROCEDE DE FABRICATION DE COMPOSES COMPRENANT DES FONCTIONS  PROCESS FOR PRODUCING COMPOUNDS COMPRISING FUNCTIONS
NITRILES [0001] La présente invention concerne la fabrication de composés comprenant des fonctions nitriles et de composés imide cycliques.  The present invention relates to the manufacture of compounds comprising nitrile functions and cyclic imide compounds.
[0002] Elle se rapporte plus particulièrement à la fabrication de composés comprenant des fonctions nitriles à partir de composés comprenant des fonctions carboxyliques, avantageusement d'origine naturelle et renouvelable, et à partir d'un mélange N de dinitriles comprenant du méthyl-2 glutaronitrile (MGN), de l'éthyl-2 succinonitrile (ESN) et de l'adiponitrile (AdN).  It relates more particularly to the manufacture of compounds comprising nitrile functions from compounds comprising carboxylic functions, preferably of natural and renewable origin, and from an N mixture of dinitriles comprising 2-methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN) and adiponitrile (AdN).
[0003] Les composés comprenant des fonctions nitriles sont des produits importants pour la fabrication de composés aminés. Les composés dinitriles conduisent à des aminés qui sont par exemple des monomères à l'origine de polymères tels que le polyamide, par exemple. Les composés mononitriles conduisent à des aminés ou à des amides qui sont par exemple utilisés pour la fabrication de tensioactifs cationiques.  [0003] Compounds comprising nitrile functions are important products for the manufacture of amine compounds. The dinitrile compounds lead to amines which are, for example, monomers which are the origin of polymers such as polyamide, for example. The mononitrile compounds lead to amines or amides which are for example used for the manufacture of cationic surfactants.
[0004] De nombreux procédés de synthèse de nitriles ont été proposés, notamment des procédés de synthèse à partir d'ammoniac et d'acides carboxyliques. Ces procédés utilisent principalement comme matière première de départ des composés hydrocarbures issus du raffinage du pétrole, et de l'ammoniac, qui est obtenu à partir d'hydrogène provenant de procédés de vaporéformage qui consomment du gaz et de l'énergie.  Many nitrile synthesis processes have been proposed, including synthetic processes from ammonia and carboxylic acids. These processes mainly use hydrocarbon compounds derived from petroleum refining, and ammonia, which are obtained from hydrogen from steam reforming processes that consume gas and energy, as starting material.
[0005] Compte tenu de l'épuisement de la ressource pétrolière, de nombreux travaux de recherche sont entrepris pour développer des procédés de synthèse de ces composés, importants pour la fabrication de matériaux utilisés dans de nombreuses applications, à partir de matières premières ou ressources dites renouvelables, ou à partir de matières premières recyclées, qui sont habituellement détruites ou valorisées uniquement sous forme d'énergie. Ces ressources renouvelables peuvent être produites à partir de matière végétale cultivée ou non telle que les arbres, les plantes comme la canne à sucre, le maïs, le manioc, le blé, le colza, le tournesol, la palme, le ricin ou analogues.  Given the depletion of the oil resource, many research is being undertaken to develop synthetic processes for these compounds, important for the manufacture of materials used in many applications, from raw materials or resources so-called renewable, or from recycled raw materials, which are usually destroyed or valorized only in the form of energy. These renewable resources can be produced from plant material grown or not, such as trees, plants such as sugar cane, maize, cassava, wheat, rapeseed, sunflower, palm, castor oil or the like.
[0006] Cette matière végétale est transformée par des procédés comprenant généralement plusieurs étapes mécaniques, chimiques et biologiques.  This plant material is transformed by methods generally comprising several mechanical, chemical and biological steps.
[0007] Par ailleurs, à propos des matières premières recyclées, la fabrication de l'adiponitrile, un grand intermédiaire chimique utilisé notamment dans la synthèse de l'hexaméthylène diamine et du caprolactame (monomères pour la fabrication des polyamides), obtenu par hydrocyanation du butadiène, génère un flux de sous-produits dinitriles comprenant majoritairement des composés dinitriles ramifiés comme le méthyl-2 glutaronitrile, l'éthyl-2 succinonitrile. Ce mélange de composés dinitriles ramifiés est obtenu par distillation pour le séparer de l'adiponitrile. Comme la séparation n'est généralement pas complète, le mélange de composés dinitriles ramifiés peut comprendre également une faible proportion d'adiponitrile. [0007] Moreover, with regard to recycled raw materials, the manufacture of adiponitrile, a large chemical intermediate used in particular in the synthesis of hexamethylene diamine and caprolactam (monomers for the manufacture of polyamides), obtained by hydrocyanation of butadiene, generates a stream of dinitrile byproducts comprising predominantly branched dinitrile compounds such as 2-methylglutaronitrile, 2-ethylsuccinonitrile. This mixture of branched dinitrile compounds is obtained by distillation to separate it from adiponitrile. Since the separation is generally not complete, the mixture of branched dinitrile compounds may also comprise a small proportion of adiponitrile.
[0008] Plusieurs solutions ont été proposées pour valoriser ces sous-produits ou mélanges. Une de celles-ci consiste à hydrogéner les composés dinitriles en aminés primaires notamment pour produire de la méthyl-2 pentaméthylènediamine (MPMD), utilisée comme monomère pour la fabrication de polyamides particuliers ou comme intermédiaire pour la production de vitamine B3 (nicotinamide). Several solutions have been proposed to value these by-products or mixtures. One of these consists in hydrogenating the dinitrile compounds into primary amines in particular to produce 2-methylpentamethylenediamine (MPMD), used as a monomer for the manufacture of particular polyamides or as an intermediate for the production of vitamin B3 (nicotinamide).
Ce procédé requiert des étapes de purification du méthyl-2 glutaronitrile et de la méthyl-2 pentaméthylènediamine. This process requires purification steps of 2-methylglutaronitrile and 2-methylpentamethylenediamine.
[0009] Dans l'industrie, ces sous-produits sont également valorisés sous forme de vapeur ou d'énergie par combustion. Toutefois, cette combustion peut demander un traitement des gaz pour éliminer les oxydes d'azote produits et elle produit du gaz carbonique qui est rejeté dans l'atmosphère. In the industry, these by-products are also recovered in the form of steam or energy by combustion. However, this combustion may require a gas treatment to remove the nitrogen oxides produced and it produces carbon dioxide that is released into the atmosphere.
[0010] Il existe donc un besoin et une demande importante de trouver de nouvelles voies de valorisation et transformation de ces composés dinitriles ou des mélanges en composés chimiques valorisâmes et économiquement intéressants.  There is therefore a need and a significant demand to find new ways of recovery and processing of these dinitrile compounds or mixtures of valuable chemical compounds and economically interesting.
[001 1] A cet effet, l'invention propose un procédé de préparation d'au moins un nitrile de formule générale I [001 1] For this purpose, the invention provides a process for the preparation of at least one nitrile of general formula I
ou respectivement d'au moins un nitrile de formule générale III or respectively at least one nitrile of general formula III
et d'au moins l'imide cyclique 3-méthyl-glutarimide, and at least the cyclic imide 3-methylglutarimide,
par réaction entre au moins un acide carboxylique de formule générale II respectivement au moins un a formule générale by reaction between at least one carboxylic acid of general formula II respectively at least one general formula
et au moins le méthyl-2 glutaronitrile (MGN), and at least 2-methylglutaronitrile (MGN),
avec with
y est égal à 1 ou 2 y is 1 or 2
R représente un atome d'hydrogène ou un ou plusieurs substituants  R represents a hydrogen atom or one or more substituents
[0012] Avantageusement on met en œuvre un mélange N de dinitriles comprenant du méthyl-2 glutaronitrile (MGN), de l'éthyl-2 succinonitrile (ESN) et de l'adiponitrile (AdN). On obtient alors au moins les imides cycliques 3-méthyl-glutarimide et 3-éthyl- succinimide. Advantageously, an N mixture of dinitriles comprising 2-methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN) and adiponitrile (AdN) is used. At least the cyclic imides 3-methylglutarimide and 3-ethylsuccinimide are obtained.
[0013] De préférence le mélange N de dinitriles est un mélange issu du procédé de fabrication de l'adiponitrile par double hydrocyanation du butadiène. Il correspond de préférence à la fraction de distillation permettant de séparer les dinitriles ramifiés (méthyl-2 glutaronitrile, éthyl-2 succinonitrile) de l'adiponitrile.  [0013] Preferably the N mixture of dinitriles is a mixture resulting from the process for the manufacture of adiponitrile by double hydrocyanation of butadiene. It preferably corresponds to the distillation fraction making it possible to separate the branched dinitriles (2-methylglutaronitrile, 2-ethylsuccinonitrile) from adiponitrile.
[0014] Ce mélange de dinitriles a généralement la composition pondérale suivante :  This mixture of dinitriles generally has the following composition by weight:
Méthyl-2 glutaronitrile : comprise entre 70 % et 95 %, de préférence entre 80 et 85%  2-methylglutaronitrile: between 70% and 95%, preferably between 80 and 85%
Ethyl-2 succinonitrile : compris entre 5 % et 30 %, de préférence entre 8 et 2-Ethyl succinonitrile: between 5% and 30%, preferably between 8 and
12% 12%
Adiponitrile : compris entre 0 % et 10 % , de préférence entre 1 et 5% le complément à 100% correspondant à différentes impuretés  Adiponitrile: between 0% and 10%, preferably between 1 and 5%, the 100% complement corresponding to different impurities
[0015] Le procédé de l'invention met en œuvre un acide carboxylique de formule générale II telle que décrite ci-dessus.  The process of the invention uses a carboxylic acid of general formula II as described above.
[0016] Avantageusement l'acide carboxylique de formule générale II ou IV est issu d'une matière renouvelable d'origine végétale.  Advantageously, the carboxylic acid of general formula II or IV is derived from a renewable material of vegetable origin.
[0017] Une matière ou ressource renouvelable est une ressource naturelle, animale ou végétale, dont le stock peut se reconstituer sur une période courte à l'échelle humaine. Il faut en particulier que ce stock puisse se renouveler aussi vite qu'il est consommé. [0018] A la différence des matériaux issus de matières fossiles, les matières premières renouvelables contiennent une proportion importante de 14C. De préférence les nitriles de l'invention sont constitués de carbone organique issu de matières premières renouvelables. Ainsi cette caractéristique préférée pourrait être certifiée par détermination de la teneur en 14C selon l'une des méthodes décrites dans la norme ASTM D6866, notamment selon la méthode par spectrométrie de masse ou la méthode par spectrométrie à scintillation liquide qui sont décrites dans cette norme. A material or renewable resource is a natural resource, animal or plant, whose stock can be reconstituted over a short period on a human scale. In particular, this stock must be renewed as quickly as it is consumed. Unlike materials from fossil materials, renewable raw materials contain a significant proportion of 14 C. Preferably the nitriles of the invention consist of organic carbon from renewable raw materials. Thus, this preferred characteristic could be certified by determination of the 14 C content according to one of the methods described in the ASTM D6866 standard, in particular according to the mass spectrometry method or the liquid scintillation spectrometry method which are described in this standard. .
[0019] Ces ressources renouvelables peuvent être produites à partir de matière végétale cultivée ou non telle que les arbres, les plantes comme la canne à sucre, le maïs, le manioc, le blé, le colza, le tournesol la palme, le ricin ou analogues. These renewable resources can be produced from plant material grown or not such as trees, plants such as sugar cane, corn, cassava, wheat, rapeseed, sunflower palm, castor or like.
[0020] Par exemple, l'acide carboxylique de formule générale II ou IV peut être issu de ressources renouvelables tels que les polysaccharides naturels comme par exemple l'amidon ou la cellulose, l'amidon pouvant être extrait, par exemple, du maïs, du blé ou de la pomme de terre. Il peut en particulier provenir de divers procédés de transformation, notamment de procédés chimiques classiques, de procédés de transformation par voie enzymatique ou encore par fermentation.  For example, the carboxylic acid of general formula II or IV may be derived from renewable resources such as natural polysaccharides such as starch or cellulose, the starch being able to be extracted, for example, from maize, wheat or potato. It can in particular come from various transformation processes, including conventional chemical processes, enzymatic transformation processes or by fermentation.
[0021] L'acide 2,5-furannedicarboxylique peut par exemple être obtenu à partir de l'acide mucique ou à partir de l'hydroxyméthylfurfural.  2,5-Furannedicarboxylic acid can for example be obtained from mucic acid or from hydroxymethylfurfural.
[0022] Avantageusement R est choisi parmi : [0022] Advantageously, R is chosen from:
- les groupes alkyle linéaires ou ramifiés ayant de préférence de 1 à 6 atomes de carbone et encore plus préférentiellement de 1 à 4 atomes de carbone, the linear or branched alkyl groups preferably having from 1 to 6 carbon atoms and even more preferentially from 1 to 4 carbon atoms,
- les groupes alkyle mono-, poly- ou perhalogénés, linéaires ou ramifiés ayant de préférence de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène et encore plus préférentiellement de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène,  the linear or branched mono, poly or perhalogenated alkyl groups preferably having from 1 to 6 carbon atoms and from 1 to 13 halogen atoms and even more preferably from 1 to 4 carbon atoms and from 1 to 9 carbon atoms; halogen atoms,
- les groupes éther R2-0- ou thioéther R2-S- dans lesquels R2 représente un groupe alkyle linéaire ou ramifié ayant de 1 à 6 atomes de carbone et encore plus préférentiellement de 1 à 4 atomes de carbone ou le groupe phényle , the ether groups R 2 -O- or thioether R 2 -S- in which R 2 represents a linear or branched alkyl group having from 1 to 6 carbon atoms and even more preferably from 1 to 4 carbon atoms or the phenyl group ,
- les groupes acyloxy ou aroyloxy R2-CO-0- dans lesquels le groupe R2 a la signification donnée précédemment, the acyloxy or aroyloxy groups R 2 -CO-O- in which the group R 2 has the meaning given above,
- les groupes acyle ou aroyie R2-CO- dans lesquels le groupe R2 a la signification donnée précédemment, the acyl or aroyl groups R 2 -CO- in which the group R 2 has the meaning given above,
- le groupe hydroxyle,  the hydroxyl group,
- un atome d'halogène, de préférence, un atome de fluor.  a halogen atom, preferably a fluorine atom.
[0023] Selon un mode de réalisation particulier de l'invention, y est égal à 1 et R représente -CO-0-R3 avec R3 qui représente un groupe alkyle ayant de 1 à 4 atomes de carbone dans la formule générale II ou IV According to a particular embodiment of the invention, y is 1 and R represents -CO-O-R 3 with R 3 which represents an alkyl group having 1 to 4 carbon atoms in the general formula II or IV
[0024] De préférence le composé de formule II ou IV est choisi parmi l'acide 2,5- furannedicarboxylique, l'acide 2,5-tetrahydrofurannedicarboxylique, l'acide 2-furoïque, l'acide 2,5-furannedicarboxylique monométhylester ou les acides 2,5- tetrahydrofurannedicarboxylique monométhylester. Preferably the compound of formula II or IV is selected from 2,5-furannedicarboxylic acid, 2,5-tetrahydrofurannedicarboxylic acid, 2-furoic acid, 2,5-furannedicarboxylic acid monomethyl ester or 2,5-tetrahydrofuranyl dicarboxylic acid monomethyl ester.
[0025] Le composé de formule IV, lorsqu'il s'agit d'un diacide (y=2) ou d'un composé comprenant une fonction acide et une fonction ester (y=1 et R représente -CO-0-R3 avec R3 qui représente un groupe alkyle ayant de 1 à 4 atomes de carbone dans la formule générale IV), peut être mis en œuvre dans la réaction de l'invention sous forme d'un seul isomère (par exemple l'isomère cis ou l'isomère trans) ou sous la forme d'un mélange d'isomères (par exemple un mélange de l'isomère cis et de l'isomère trans). A titre d'illustration, lorsque le composé de formule IV est le 2,5- tetrahydrofurannedicarboxylique acide, il peut être mis en œuvre sous la forme de l'isomère trans, de l'isomère cis ou d'un mélange de l'isomère cis et de l'isomère trans. The compound of formula IV, when it is a diacid (y = 2) or a compound comprising an acid function and an ester function (y = 1 and R represents -CO-O-R 3 with R 3, which represents an alkyl group having from 1 to 4 carbon atoms in the general formula IV), can be used in the reaction of the invention as a single isomer (for example the cis isomer or the trans isomer) or in the form of a mixture of isomers (for example a mixture of the cis-isomer and the trans-isomer). By way of illustration, when the compound of formula IV is 2,5-tetrahydrofurannedicarboxylic acid, it can be used in the form of the trans isomer, the cis isomer or a mixture of the isomer cis and trans isomer.
[0026] Dans le cadre du procédé de l'invention, on peut mettre en œuvre un mélange de plusieurs acides carboxyliques, par exemple un acide carboxylique de formule générale II ou IV et un autre acide carboxylique, ou un mélange de plusieurs acides carboxyliques de formule II ou IV. In the context of the process of the invention, it is possible to use a mixture of several carboxylic acids, for example a carboxylic acid of general formula II or IV and another carboxylic acid, or a mixture of several carboxylic acids of formula II or IV.
[0027] Le procédé de l'invention est avantageusement mis en œuvre à une température comprise entre 150 et 350°C. La pression mise en œuvre est généralement comprise entre la pression atmosphérique et quelques bars.  The process of the invention is advantageously carried out at a temperature of between 150 and 350 ° C. The pressure used is generally between atmospheric pressure and a few bars.
[0028] Des catalyseurs peuvent être mis en œuvre dans le cadre du procédé de l'invention. A titre d'exemple de catalyseurs, on peut citer l'acide phosphorique, les phosphates, les borophosphates, l'acide sulfurique, l'acide sulfonique, les acide benzène sulfonique, les acide toluène sulfonique tels que l'acide para toluène sulfonique, les acides naphtalène sulfoniques, la silice, l'alumine, l'argile, la silice/alumine.  Catalysts can be implemented in the context of the process of the invention. As examples of catalysts, mention may be made of phosphoric acid, phosphates, borophosphates, sulfuric acid, sulphonic acid, benzene sulphonic acid, toluene sulphonic acid, such as para toluene sulphonic acid, naphthalene sulfonic acids, silica, alumina, clay, silica / alumina.
[0029] De façon avantageuse, on met en œuvre une quantité de méthyl-2 glutaronitrile (MGN) ou de mélange N de telle sorte qu'au moins une molécule de méthyl- 2 glutaronitrile (MGN) ou d'éthyl-2 succinonitrile (ESN) est introduite dans le milieu réactionnel, par fonction acide de l'acide carboxylique de formule générale II ou IV à transformer en fonction nitrile. Advantageously, a quantity of 2-methylglutaronitrile (MGN) or of mixture N is used such that at least one molecule of 2-methylglutaronitrile (MGN) or 2-ethylsuccinonitrile ( ESN) is introduced into the reaction medium, by acid function of the carboxylic acid of general formula II or IV to be converted into a nitrile function.
[0030] Lorsque l'on met en œuvre un diacide comme acide de formule générale II ou IV, on peut obtenir le dinitrile correspondant ou le nitrile acide correspondant (par exemple en mettant en œuvre un défaut de fonction nitrile).  When a diacid is used as the acid of general formula II or IV, it is possible to obtain the corresponding dinitrile or the corresponding acidic nitrile (for example by implementing a defect in nitrile function).
[0031] Lors de la réaction entre le composé de formule (II) ou (IV) et le mélange N de dinitriles conformément à l'invention, des imides sont formés, notamment le 3- méthyl glutarimide issu du MGN et le 3-éthylsuccinimide issu de l'ESN.  During the reaction between the compound of formula (II) or (IV) and the N mixture of dinitriles according to the invention, imides are formed, in particular 3-methylglutarimide from MGN and 3-ethylsuccinimide from the ESN.
[0032] Avantageusement, le procédé de l'invention comprend également une étape de récupération d'au moins le nitrile de formule (I) ou (III) d'une part, et d'au moins l'imide cyclique d'autre part, à partir du milieu réactionnel. [0033] Cette récupération peut être réalisée par séparation des composés du milieu réactionnel, selon toute méthode connue telle que la distillation. Advantageously, the process of the invention also comprises a step of recovering at least the nitrile of formula (I) or (III) on the one hand, and at least the cyclic imide on the other hand from the reaction medium. This recovery can be carried out by separation of the compounds of the reaction medium, according to any known method such as distillation.
[0034] Selon un premier mode de réalisation avantageux, les composés peuvent être obtenus par distillation réactive. En effet lorsque le nitrile de formule (I) ou (III) que l'on souhaite obtenir a une température d'ébullition inférieure à celle de la température de réaction (ce qui est en particulier le cas pour les nitriles ayant un faible nombre de carbones), on peut distiller ce nitrile au fur et à mesure de sa formation, ce qui déplace l'équilibre de la réaction en faveur de la formation de ce nitrile ; ceci est donc particulièrement avantageux. Cette méthode de distillation réactive peut par exemple être utilisée lorsque le nitrile de formule (I) ou (III) est le 2,5-dicyanotetrahydrofuranne ou un mononitrile. According to a first advantageous embodiment, the compounds can be obtained by reactive distillation. Indeed, when the nitrile of formula (I) or (III) that it is desired to obtain has a boiling point lower than that of the reaction temperature (which is particularly the case for nitriles having a low number of carbons), this nitrile can be distilled as it is formed, displacing the equilibrium of the reaction in favor of the formation of this nitrile; this is therefore particularly advantageous. This reactive distillation method may for example be used when the nitrile of formula (I) or (III) is 2,5-dicyanotetrahydrofuran or a mononitrile.
[0035] Selon un deuxième mode de réalisation avantageux, les composés peuvent être séparés par extraction à l'eau chaude. En effet les imides sont généralement solubles dans l'eau, contrairement notamment aux nitriles, ce qui permet une bonne séparation par une voie aisée à mettre en œuvre. Cette voie est à privilégier notamment lorsque les nitriles et les imides à séparer ont des températures d'ébullition qui sont proches et qu'ils sont par ce fait difficile à séparer par distillation classique par exemple. La température de l'eau lors de cette extraction est généralement supérieure ou égale à 50°C.  According to a second advantageous embodiment, the compounds can be separated by extraction with hot water. Indeed the imides are generally soluble in water, unlike nitriles, which allows a good separation by an easy way to implement. This route is preferred especially when the nitriles and imides to be separated have boiling temperatures that are close and they are therefore difficult to separate by conventional distillation, for example. The temperature of the water during this extraction is generally greater than or equal to 50 ° C.
[0036] Selon un mode de réalisation particulier de l'invention, le nitrile de formule (I) ou (III) ainsi récupéré est hydrogéné pour former l'aminé correspondante, selon une méthode connue de l'homme du métier. Lorsque l'on récupère un nitrile de formule (I), son hydrogénation peut conduire à l'aminé correspondant au composé de formule (III), par hydrogénation non seulement de la fonction nitrile, mais également par hydrogénation des doubles liaisons du cycle furannique. Ainsi on obtient une aminé dont tous les carbones sont biosourcés (car issus d'un acide carboxylique biosourcé, c'est-à-dire un acide carboxylique issu d'une matière première renouvelable), et dont les atomes d'azote sont recyclés (car issus de sous-produits habituellement brûlés ce qui génère du dioxyde de carbone et des oxydes d'azote, gaz à effet de serre qu'il faut traiter pour satisfaire la législation en vigueur). Les diamines peuvent être utilisées comme matières premières pour la fabrication des polyamides, qui seront ainsi partiellement ou complètement biosourcés en fonction des acides utilisés pour la polymérisation. Les aminés peuvent également être utilisées pour préparer des tensioactifs. According to a particular embodiment of the invention, the nitrile of formula (I) or (III) thus recovered is hydrogenated to form the corresponding amine, according to a method known to those skilled in the art. When a nitrile of formula (I) is recovered, its hydrogenation can lead to the amine corresponding to the compound of formula (III), by hydrogenation not only of the nitrile function, but also by hydrogenation of the double bonds of the furan ring. Thus an amine is obtained in which all the carbons are biobased (because derived from a biosourced carboxylic acid, that is to say a carboxylic acid derived from a renewable raw material), and whose nitrogen atoms are recycled ( as derived from by-products usually burned which generates carbon dioxide and oxides of nitrogen, greenhouse gases that must be treated to meet the legislation in force). The diamines can be used as raw materials for the manufacture of polyamides, which will thus be partially or completely biobased depending on the acids used for the polymerization. Amines can also be used to prepare surfactants.
[0037] Selon un autre mode de réalisation particulier de l'invention, on peut faire réagir l'imide cyclique récupéré selon le procédé de l'invention, avec un alcool pour former le diester correspondant. Un tel procédé est connu et notamment décrit dans le document WO2008/009792 et WO 2009/056477. Les diesters peuvent être utilisés comme solvants. According to another particular embodiment of the invention, the cyclic imide recovered according to the process of the invention can be reacted with an alcohol to form the corresponding diester. Such a process is known and in particular described in WO2008 / 009792 and WO 2009/056477. The diesters can be used as solvents.
[0038] D'autres détails ou avantages de l'invention apparaîtront plus clairement à la vue des exemples donnés ci-dessous. Other details or advantages of the invention will appear more clearly in view of the examples given below.
EXEMPLES EXAMPLES
Exemple 1 : Préparation du 2,5-dicyanofuranne  Example 1 Preparation of 2,5-dicyanofuran
Dans un réacteur de 500 ml , on introduit 156g d'acide 2,5-furannedicarboxylique et 250g de 2-méthylglutaronitrile (MGN). On agite et on chauffe le milieu réactionnel qui devient homogène à 275°C. On maintient pendant 2h30 dans ces conditions. Après refroidissement, on analyse par CPG le milieu réactionnel. In a 500 ml reactor, 156 g of 2,5-furannedicarboxylic acid and 250 g of 2-methylglutaronitrile (MGN) are introduced. The reaction mixture is stirred and heated, which becomes homogeneous at 275 ° C. We maintain for 2:30 under these conditions. After cooling, the reaction medium is analyzed by GC.
La conversion du MGN est de 25% et le rendement en 3-méthylglutarimide de 18%. Le rendement en 2,5-dicyanofuranne est de 3%. The conversion of MGN is 25% and the yield of 3-methylglutarimide is 18%. The yield of 2,5-dicyanofuran is 3%.
Exemple 2 : Préparation du 2,5-dicyanofuranne Example 2 Preparation of 2,5-dicyanofuran
Dans un réacteur de 500 ml , on introduit 156g d'acide 2,5-furannedicarboxylique ,250g de 2-méthylglutaronitrile(MGN) et 2g d'acide orthophosphorique à 85% . On agite et on chauffe le milieu réactionnel qui devient homogène à 275°C. On maintient pendant 2h30 dans ces conditions. Après refroidissement, on analyse par CPG le milieu réactionnel. 500 g of 2,5-furannedicarboxylic acid, 250 g of 2-methylglutaronitrile (MGN) and 2 g of 85% orthophosphoric acid are introduced into a 500 ml reactor. The reaction mixture is stirred and heated, which becomes homogeneous at 275 ° C. We maintain for 2:30 under these conditions. After cooling, the reaction medium is analyzed by GC.
La conversion du MGN est de 75% et le rendement en 3-méthylglutarimide de 58%. Le rendement en 2,5-dicyanofuranne est de 25%.  The conversion of MGN is 75% and the yield of 3-methylglutarimide is 58%. The yield of 2,5-dicyanofuran is 25%.
Exemple 3 : Préparation du cis 2,5-tétrahydrofuranne dinitrile (THFDN) Example 3 Preparation of cis 2,5-tetrahydrofuran dinitrile (THFDN)
Dans un réacteur de 250ml, on introduit 40 g de cis 2,5-tétrahydrofuranne dicarboxylique acide (THFDCA) et 55g de 2-methylglutaronitrile. Le mélange réactionnel est alors chauffé sous agitation au reflux . On maintient le milieu réactionnel à 275°C pendant 3h30 . 250 g of cis 2,5-tetrahydrofuran dicarboxylic acid (THFDCA) and 55 g of 2-methylglutaronitrile are introduced into a 250 ml reactor. The reaction mixture is then heated with stirring under reflux. The reaction medium is maintained at 275 ° C. for 3 h 30 min.
Le milieu réactionnel est alors analysé par CPG et on obtient les résultats suivants : The reaction medium is then analyzed by GPC and the following results are obtained:
TT( MGN) = 97% TT (MGN) = 97%
TT(THFDCA) = 98% TT (THFDCA) = 98%
RR(MGI) = 97% RR (MGI) = 97%
RR(THFDN) = 90% isomère cis Exemple 4 : Préparation d'un mélange d'isomères cis + trans 2,5-tetrahydrofuranne dinitrile RR (THFDN) = 90% cis isomer EXAMPLE 4 Preparation of a mixture of cis + trans isomers 2,5-tetrahydrofuran dinitrile
Dans un réacteur de 250ml, on introduit 40 g d'un mélange cis + trans 2,5- tétrahydrofuranne dicarboxylique acide (THFDCA) et 55g de 2-methylglutaronitrile. Les deux isomères étant dans le ratio cis/trans = 80 / 20. Le mélange réactionnel est alors chauffé sous agitation au reflux . On maintient le milieu réactionnel à 275°C pendant 3h30 . 250 g of a mixture of cis + trans 2,5-tetrahydrofuran dicarboxylic acid (THFDCA) and 55 g of 2-methylglutaronitrile are introduced into a 250 ml reactor. The two isomers being in the ratio cis / trans = 80 / 20. The reaction mixture is then heated with stirring under reflux. The reaction medium is maintained at 275 ° C. for 3 h 30 min.
Le milieu réactionnel est alors analysé par CPG et on obtient les résultats suivants :  The reaction medium is then analyzed by GPC and the following results are obtained:
TT(MGN) = 98% TT (MGN) = 98%
TT (THFDCA) =97% TT (THFDCA) = 97%
RR(MGI) = 97% RR (MGI) = 97%
RR(THFDN) = 91 % isomère cis + trans (ratio cis/trans = 80 120)  RR (THFDN) = 91% cis + trans isomer (cis / trans ratio = 80 120)

Claims

REVENDICATIONS
1. Procédé de préparation d'au mo rmule générale I 1. Process for the preparation of general formula I
ou respectivement d'au moins un nitrile de formule générale III or respectively at least one nitrile of general formula III
et d'au moins l'imide cyclique 3-méthyl-glutarimide, and at least the cyclic imide 3-methylglutarimide,
par réaction entre au moins un acide carboxylique de formule générale II by reaction between at least one carboxylic acid of general formula II
ou respectivement au moins un acide carboxylique de formule générale IV or respectively at least one carboxylic acid of general formula IV
et au moins le méthyl-2 glutaronitrile (MGN), and at least 2-methylglutaronitrile (MGN),
avec with
y est égal à 1 ou 2 y is 1 or 2
R représente un atome d'hydrogène ou un ou plusieurs substituants R represents a hydrogen atom or one or more substituents
2. Procédé selon la revendication 1 , caractérisé en ce que l'on met en œuvre un mélange N de dinitriles comprenant du méthyl-2 glutaronitrile (MGN), de l'éthyl-2 succinonitrile (ESN) et de l'adiponitrile (AdN) 2. Process according to claim 1, characterized in that an N-mixture of dinitriles comprising 2-methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN) and adiponitrile (AdN) is used. )
3. Procédé selon la revendication 1 , caractérisé en ce que le mélange N de dinitriles est un mélange issu du procédé de fabrication de l'adiponitrile par double hydrocyanation du butadiène. 3. Process according to claim 1, characterized in that the N mixture of dinitriles is a mixture resulting from the process for producing adiponitrile by double hydrocyanation of butadiene.
4. Procédé selon la revendication 2 ou 3, caractérisé en ce que le mélange N de dinitriles a la composition pondérale suivante : 4. Process according to claim 2 or 3, characterized in that the N mixture of dinitriles has the following weight composition:
Méthyl-2 glutaronitrile : comprise entre 70 % et 95 %, de préférence entre 80 et 85%  2-methylglutaronitrile: between 70% and 95%, preferably between 80 and 85%
Ethyl-2 succinonitrile : compris entre 5 % et 30 %, de préférence entre 8 et 2-Ethyl succinonitrile: between 5% and 30%, preferably between 8 and
12% 12%
Adiponitrile : compris entre 0 % et 10 %, de préférence entre 1 et 5% le complément à 100% correspondant à différentes impuretés Adiponitrile: between 0% and 10%, preferably between 1 and 5%, the 100% complement corresponding to different impurities
5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le composé de formule II ou IV est issu d'une matière renouvelable d'origine végétale 5. Method according to one of the preceding claims, characterized in that the compound of formula II or IV is derived from a renewable material of plant origin
6. Procédé selon l'une des revendications précédentes, caractérisé en ce que R est choisi parmi : 6. Method according to one of the preceding claims, characterized in that R is chosen from:
- les groupes alkyle linéaires ou ramifiés ayant de préférence de 1 à 6 atomes de carbone et encore plus préférentiellement de 1 à 4 atomes de carbone, the linear or branched alkyl groups preferably having from 1 to 6 carbon atoms and even more preferentially from 1 to 4 carbon atoms,
- les groupes alkyle mono-, poly- ou perhalogénés, linéaires ou ramifiés ayant de préférence de 1 à 6 atomes de carbone et de 1 à 13 atomes d'halogène et encore plus préférentiellement de 1 à 4 atomes de carbone et de 1 à 9 atomes d'halogène,  the linear or branched mono, poly or perhalogenated alkyl groups preferably having from 1 to 6 carbon atoms and from 1 to 13 halogen atoms and even more preferably from 1 to 4 carbon atoms and from 1 to 9 carbon atoms; halogen atoms,
- les groupes éther R2-0- ou thioéther R2-S- dans lesquels R2 représente un groupe alkyle linéaire ou ramifié ayant de 1 à 6 atomes de carbone et encore plus préférentiellement de 1 à 4 atomes de carbone ou le groupe phényle , the ether groups R 2 -O- or thioether R 2 -S- in which R 2 represents a linear or branched alkyl group having from 1 to 6 carbon atoms and even more preferably from 1 to 4 carbon atoms or the phenyl group ,
- les groupes acyloxy ou aroyioxy R2-CO-0- dans lesquels le groupe R2 a la signification donnée précédemment, the acyloxy or aroyioxy groups R 2 -CO-O- in which the group R 2 has the meaning given above,
- les groupes acyle ou aroyie R2-CO- dans lesquels le groupe R2 a la signification donnée précédemment, the acyl or aroyl groups R 2 -CO- in which the group R 2 has the meaning given above,
- le groupe hydroxyle,  the hydroxyl group,
- un atome d'halogène, de préférence, un atome de fluor.  a halogen atom, preferably a fluorine atom.
7. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que y est égal à 1 et R représente -CO-0-R3 avec R3 qui représente un groupe alkyle ayant de 1 à 4 atomes de carbone dans la formule générale II ou IV 7. Method according to one of claims 1 to 5, characterized in that y is equal to 1 and R represents -CO-O-R 3 with R 3 which represents an alkyl group having 1 to 4 carbon atoms in the general formula II or IV
8. Procédé selon l'une des revendications précédentes, caractérisé en ce que le composé de formule II ou IV est l'acide 2,5-furannedicarboxylique, l'acide 2,5- tetrahydrofurannedicarboxylique, l'acide 2-furoïque, l'acide 2,5-furannedicarboxylique monométhylester ou les acides 2,5-tetrahydrofurannedicarboxylique monométhylester 8. Method according to one of the preceding claims, characterized in that the compound of formula II or IV is 2,5-furannedicarboxylic acid, 2,5-tetrahydrofurannedicarboxylic acid, 2-furoic acid, the 2,5-furannedicarboxylic acid monomethyl ester or 2,5-tetrahydrofurannedicarboxylic acid monomethyl ester
9. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'il comprend une étape de récupération d'au moins le nitrile d'une part, et d'au moins l'imide cyclique 3-méthyl-glutarimide d'autre part, par séparation des composés du milieu réactionnel 9. Method according to one of the preceding claims, characterized in that it comprises a step of recovering at least the nitrile on the one hand, and at least the cyclic imide 3-methyl-glutarimide other on the other hand, by separating the compounds from the reaction medium
10. Procédé selon la revendication 9, caractérisé en ce qu'au moins le nitrile récupéré est hydrogéné pour former l'aminé correspondante. 10. The method of claim 9, characterized in that at least the recovered nitrile is hydrogenated to form the corresponding amine.
1 1. Procédé selon la revendication 9 ou 10, caractérisé en ce que l'on fait réagir au moins l'imide cyclique 3-méthyl-glutarimide récupérée avec un alcool pour former le diester correspondant 1. Process according to claim 9 or 10, characterized in that at least the cyclic imide 3-methyl-glutarimide recovered is reacted with an alcohol to form the corresponding diester.
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US8981128B2 (en) 2015-03-17
FR2977586B1 (en) 2013-07-12
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BR112014000397A2 (en) 2016-08-23
JP2014523893A (en) 2014-09-18
FR2977586A1 (en) 2013-01-11
CN103649050A (en) 2014-03-19
US20140171663A1 (en) 2014-06-19

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