Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
  • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
  • C07D317/34—Oxygen atoms
  • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
  • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
  • C07D317/34—Oxygen atoms

Definitions

• the present invention relates to a method for synthesizing alcohol carbonate, especially glycerol carbonate.
• EP0739888 discloses a process for the preparation of glycerol carbonate by reaction of glycerol and a cyclic organic carbonate in the presence of a solid catalyst comprising a bicarbonated or hydroxylated anionic macroporous resin or a zeolite of the X or Y three-dimensional type comprising basic sites, at a temperature between 50 and 1 l O 'C.
• the yield of the reaction is of the order of 90%. To obtain this yield, it is however necessary to extract the ethylene glycol formed during the reaction.
• the process is applicable to pure glycerol as well as to glycerines.
• US2010 / 0209979 also discloses a process for the preparation of glycerol carbonate by reaction between dimethyl carbonate and glycerol by lipase catalyzed transesterification.
• JP06329663 discloses a process for preparing glycerol carbonate by reaction between ethylene carbonate and glycerol catalyzed by oxides of aluminum, magnesium, zinc, titanium, lead. Other methods have been developed by CaO catalysis.
• the catalysts of the state of the prior art generally comprise a basic entity, in particular of the metal oxide type.
• This basic entity is soluble in the presence of water or hydratable (undergoes a reaction with water) which deteriorates its effectiveness. It is therefore important to control the reaction medium, and especially the amount of water, to implement such catalysts.
• the present invention relates to a process for the preparation by transcarbonation of a compound of formula (I),
• ⁇ R 1 represents:
• a hydrogen atom a linear, branched or cyclic C 1 to C 9 , preferably C 1 to C 5 , hydrocarbon group which may comprise one or more heteroatoms, chosen in particular from oxygen, nitrogen or sulfur, and which may comprise a or more OH substituents;
• R 3 represents a hydrocarbon group, Ci-C 9 , preferably Ci-C 5 , linear or branched, which may comprise one or more heteroatoms, in particular chosen from oxygen, nitrogen or sulfur, and may include one or more OH substituents;
• a C 5 to C 14 preferably C 6 to C 14 , preferably C 6 to C 10 , aryl group, optionally substituted, in particular with a C 1 to C 9 , preferably C 1 to C 5, alkyl group; ; a C 5 to C 14 , preferably C 6 to C 14 , preferably C 6 to C 6 aryl group which is optionally substituted; an alkyl-aryl group of formula -Q 2 -Ar 2 in which Q 2 represents a C 1 to C 9 alkyl residue, preferably d to and Ar 2 represents a C 6 to C 14 , preferably C, aryl group; 6 , optionally substituted; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of at d 0, preferably d-d; alkoxy of -C 9, preferably d; or
• a heteroaryl group preferably comprising from 5 to 10 members, optionally substituted, in particular with: a C 1 to C 9 alkyl group, preferably a d to C 9 alkyl group; an aryl group having from 1 to 4 , preferably from 1 to 4 , preferably from 1 to 6 , optionally substituted; an alkyl-aryl group of formula -Q 3 -Ar 3 in which Q 3 represents a C 1 to C 9 alkyl residue, preferably d to and Ar 3 represents an aryl radical in C to C 4 , preferably in optionally substituted ; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of to 10 C, preferably d; alkoxy of -C 9, preferably C 5 d; ⁇ R 2 represents:
• alkyl group linear or branched, in d to C 10 , preferably in d to;
• a hydrocarbon group in d, preferably d-d, linear, branched or cyclic, may include one or more heteroatoms, especially chosen from oxygen, nitrogen or sulfur, and which may comprise one or more OH substituents; an alkyl-aryl group of formula -Q 4 -Ar 4 wherein Q 4 represents an alkyl residue to C 9, preferably C, to C 5 and Ar 4 represents an aryl group of C 6 to 4, preferably C 6 , optionally substituted;
• hydrocarbon group in d -C 9, preferably d -C 5 linear, branched or cyclic, may include one or more heteroatoms, in particular selected from oxygen, nitrogen or sulfur, and may include a or more pendant OH groups;
• a C 5 to C 14 preferably C 6 to C 14 , preferably C 6 to C 10 , aryl group, optionally substituted, in particular with a C 1 to C 9 , preferably C 1 to C 5, alkyl group; ; an aryl group of C 5 -C 14, preferably C 6 to C 4, preferably C 6 to 0, optionally substituted; an alkyl-aryl group of the formula -Q 5 -Ar 5 in which Q 5 represents an alkyl residue in d to 9 , preferably in d to d and Ar 5 is a C 1 to C 4 aryl group, preferably in the form of optionally substituted; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of at d 0, preferably d; an alkoxy group, in the range of d to preferably in d;
• a heteroaryl group optionally substituted, in particular with a C 1 to C 9 alkyl group, preferably a d to C alkyl group; a C 1 -C 14 , preferably C 1 -C 4 , preferably C 1 -C 10 , aryl group which is optionally substituted; an alkyl-aryl group of formula -Q 6 -Ar 6 in which Q 6 represents an alkyl residue in d to C 9 , preferably in d to and Ar 6 represents an aryl in C 14 , preferably in d, optionally substituted; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group Ci-Ci 0, preferably C l -C 5; a C 1 -C 9 , preferably C 1 -C 5 , alkoxy group
• an aryl group C 5 to 4, preferably C 6 to 4, preferably C 6 to C 0, optionally substituted, especially by alkyl to C 9, preferably C, to C 5 ; a C 5 to C 4 , preferably C 6 to C 4 , preferably C 6 to C 10 , aryl group which is optionally substituted; an alkyl-aryl group of the formula - Q 5 -Ar 5 in which Q 5 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 5 represents a C 6 to C 6 aryl group;
• n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5 d; an alkoxy group of from 1 to 9 carbon atoms , preferably from 1 to 5 carbon atoms ; or
• a heteroaryl group preferably comprising 5 to 10 membered, optionally substituted, especially by alkyl to C 9, preferably C l -C 5; a C 5 to C 14 , preferably C 6 to C 14 , preferably C 6 to C 10 , aryl group which is optionally substituted; an alkyl-aryl group of formula -Q 6 -
• Ar 6 wherein Q 6 represents an alkyl residue to C 9, preferably C, to C 5 and Ar 6 represents an aryl group, C 6 to C 4, preferably C 6, optionally substituted; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5 d; an alkoxy group, in the range of from C to C 9 , preferably from C to C 5
• R 1 represents:
• R 3 represents a linear or branched C 1 to C 9 , preferably d to C 5 , alkyl group which may comprise one or more heteroatoms, chosen in particular from oxygen, nitrogen or sulfur, and may include one or more OH substituents; preferably methylene, ethylene;
• a phenyl group optionally substituted, in particular with: a C 1 to C 9 alkyl group, preferably a C 5 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of formula -Q 2 -Ar 2 in which Q 2 represents an alkyl residue in d to C 9 , preferably in d to and Ar 2 represents an optionally substituted phenyl group, for example methylphenyl, ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of at d 0, preferably d-d; an alkoxy group, d to d, for example methoxy, ethoxy;
• a cycloalkyl group which is optionally substituted, in particular with a C 1 to C 4 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of formula -Q 7 -Ar 7 in which Q 7 represents an alkyl residue in d to C 9 , preferably in d to and Ar 7 represents an optionally substituted phenyl group, preferably methylphenyl, ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of to 10 C, preferably d; a C 1 -C 5 alkoxy group, for example methoxy, ethoxy; or
• a heteroaryl group of pyridinyl or thiophenyl type optionally substituted, in particular with a C 1 to C 4 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of formula -Q 3 -Ar 3 in which Q 3 represents a C 9 to C 9 alkyl residue, preferably d to and Ar 3 represents an optionally substituted phenyl group, for example methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer of 2 to 5 and R 15 is C 1 to C 10 , preferably C 1 to C 5 , alkyl; alkoxy Ci to C 5, for example methoxy, ethoxy.
• R 2 represents:
• a linear or branched C 1 -C 9 preferably C 1 -C 5 , alkyl group, for example methyl, ethyl or propyl;
• a linear or branched C 1 to C 9 preferably C 1 to C 5 , alkyl group which may comprise one or more heteroatoms, chosen in particular from oxygen, nitrogen or sulfur, and which may comprise one or more groups; OH during;
• a phenyl group optionally substituted, in particular with a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of the formula -Q 5 -Ar 5 in which Q 5 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 5 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of to preferably d -C 5; a C 5 to C 5 alkoxy group, for example methoxy, ethoxy;
• a C 5 to C 6 cycloalkyl group optionally substituted, in particular with a C 1 to C 5 alkyl group, for example methyl, ethyl; an optionally substituted phenyl group; an arylalkyl group of formula -Q 8 -Ar 8 in which Q 8 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 8 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5 d; a C 5 to C 5 alkoxy group, for example methoxy, ethoxy; - a heteroaryl group such thiophenyl or pyridinyl, optionally substituted, especially by alkyl to C 5, for example methyl, ethy
• phenyl optionally substituted, especially by alkyl to C 5, for example methyl, ethyl; an optionally substituted phenyl group; an alkyl-aryl group of the formula -Q 5 -Ar 5 in which Q 5 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 5 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5 d; a C 5 to C 5 alkoxy group, for example methoxy, ethoxy; a C 5 to C 6 cycloalkyl group optionally substituted, in particular with a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an arylal
• the polyol may be chosen from ethylene glycol, propylene glycol, glycerol, erythritol, sorbitol, and the compound of formula (I) is the corresponding compound.
• R 2 represents a group of formula -L 1 OH.
• the compound of formula (I) is a compound of formula (Ia)
• polyol of formula (II) is a polyol of formula (IIa)
• R 1 and L 1 have the above-mentioned definitions.
• L 1 is a linear or branched alkyl radical comprising at least one -OH substituent.
• the polyol is a polyglycerol.
• the compound of formula (I) is glycerol carbonate, of the following formula
• the polyol is glycerol.
• the alkyl carbonate may be a compound of formula
• R 4 and R 5 which are identical or different, represent:
• a C 5 to C 4 preferably C 6 to C 4 , aryl group optionally substituted, in particular, with a C 1 to C 9 , preferably C 1 to C 5 , alkyl group; aryl, C 5 -C, preferably C 6 to 4, preferably C 6 to C 1 0; optionally substituted alkyl-aryl group of formula -Q 9 -Ar 9 wherein Q 9 represents an alkyl residue to C 9, preferably C 5 -C 9 and Ar represents an aryl group of C 6 to 4, preferably C 6 , optionally substituted; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5; alkoxy of -C 9, preferably C 5 d; a C 5 to C 6 cycloalkyl group optionally substituted, in particular with a C 1 to C 9 , preferably C 1 to C 5 , alkyl
• a heteroaryl group preferably comprising 5 to 10 members, optionally substituted in particular with a C 1 to C 9 , preferably C 1 to C 5 , alkyl group; a C 5 to C 14 , preferably C 6 to C 14 , preferably C 6 to C 10 , aryl group which is optionally substituted; an alkyl-aryl group of the formula -Q 11 -Ar 11 in which Q 11 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 11 represents a C 6 -C 14 aryl group, preferably C 6 , optionally substituted; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 is alkyl to C 10, preferably C l -C 5; an alkoxy group -C 9, preferably C l -C 5;
• R 4 and R 5 which are identical or different, represent:
• a linear or branched C 1 -C 10 alkyl group for example methyl, ethyl, propyl or butyl;
• a C 6 , C 10 or C 14 aryl group optionally substituted in particular with a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of the formula -Q 9 -Ar 9 in which Q 9 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 9 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5 d; a C 5 to C 5 alkoxy group, for example methoxy, ethoxy;
• a heteroaryl group of aniline type optionally substituted in particular with a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of formula -Q 11 -Ar 11 in which Q 11 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 11 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 is alkyl to C 10, preferably C 5 d; a C 5 to C 5 alkoxy group, for example methoxy, ethoxy;
• the alkyl carbonate is dimethyl carbonate, diethyl carbonate.
• alkylene carbonate is understood to mean a compound of formula (IV)
• R 6 , R 7 , R 8 and R 9, which are identical or different, are chosen from:
• a linear, branched or cyclic hydrocarbon group preferably in the range d to C 9 , preferably d to C 5 , which may comprise one or more heteroatoms, chosen in particular from oxygen, nitrogen or sulfur, and which may comprise one or more several OH substituents;
• a group of formula -CH 2 -R 10 in which R 10 represents a hydrocarbon group, Ci-C 9 , preferably Ci-C 5 , linear, branched or cyclic, which may comprise one or more heteroatoms, chosen in particular from oxygen, nitrogen or sulfur, and may include one or more OH substituents;
• R 11 represents a hydrogen atom, a Ci-C 9 alkyl group, preferably a Ci-C 5 alkyl group, for example methyl or ethyl;
• a C 6 to C 14 aryl group optionally substituted in particular with a C 1 to C 9 , preferably C 1 to C 5 , alkyl group; a C 5 to C 14 , preferably C 6 to C 14 , preferably C 6 to C 10 , aryl group which is optionally substituted; an alkyl-aryl group of the formula -Q 15 -Ar 15 in which Q 15 represents an alkyl residue in d to C 9 , preferably in d to C 5 and Ar 15 is a C 6 to C 14 aryl group, preferably C 6 , optionally substituted; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5 d; alkoxy of -C 9, preferably C 5 d; an alkyl-aryl group of formula -Q 16 -Ar 16 in which Q 16 represents a C 1 -C 9 ,
• R 6 and R 9 together with the carbon atoms carrying them a double bond; or R 6 and R 9 together with the carbon atoms carrying them a double bond which is included in an aryl group, especially phenyl, formed by R 7 and R 8 with the two carbon atoms carrying them.
• R 6 , R 7 , R 8 and R 9, which are identical or different, are preferably chosen from:
• R 10 represents a linear or branched C 1 -C 5 hydrocarbon-based group which may comprise one or more heteroatoms, chosen in particular from oxygen, nitrogen or sulfur, and may comprise one or more OH substituents, for example ethylene, methylene;
• R 11 represents a hydrogen atom or a C 1 -C 5 alkyl group, for example methyl or ethyl;
• a C 5 to C 6 cycloalkyl group optionally substituted, in particular by: a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of formula -Q 13 -Ar 13 in which Q 13 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 13 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5 d; a C 5 to C 5 alkoxy group, for example methoxy, ethoxy;
• a heteroaryl group of aniline type optionally substituted in particular with a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of formula -Q 14 -Ar 14 in which Q 14 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 14 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents alkyl Ci -C 10, preferably C l -C 5; alkoxy Ci to C 5, for example methoxy, ethoxy;
• R 6 and R 9 together with the carbon atoms carrying them a double bond; or R 6 and R 9 together with the carbon atoms carrying them a double bond which is included in an aryl group, especially phenyl, formed by R 7 and R 8 with the two carbon atoms carrying them.
• the alkyl carbonate may be ethylene carbonate, propylene carbonate, dibutylene carbonate, dihexylene carbonate.
• the catalytic entity of the catalytic system is a rare earth oxide or a mixture of rare earth oxides.
• Rare earth (Ln) means the chemical elements selected from the group consisting of scandium, yttrium, and chemical elements of atomic number 57 to 71.
• the rare earths are chosen from cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), yttrium (Y), gadolinium (Gd) and samarium (Sm). ) and holmium (Ho), alone or as a mixture, preferably cerium, lanthanum, praseodymium, samarium, yttrium and neodymium, or mixtures thereof.
• the catalytic entity is chosen from CeO 2 ; Pr 6 O; rare earth oxides of formula Ln 2 0 3 wherein Ln represents lanthanum, neodymium, yttrium, gadolinium, samarium or holmium; or in mixture.
• the catalytic entity is chosen from La 2 0 3 , Ce0 2 , Pr 6 On, Nd 2 0 3 , Sm 2 0 3 , Y 2 0 3 , alone or as a mixture, preferably La 2 0 3 .
• a mixture mention may be made especially of natural mixtures of rare earth oxides.
• CeO 2 / Pr 6 0n mention may for example be made of CeO 2 / Pr 6 0n.
• the catalytic entity is La 2 0 3 .
• the catalytic entity is CeO 2 .
• the catalytic system according to the invention consists of a catalytic entity in solid form, thus allowing its use in a continuous process.
• the catalyst may in particular be in monolithic form (forming a single inert block, rigid, porous) or in extruded form.
• the catalyst system may also comprise an inert support on which the catalytic entity is deposited.
• the catalytic system comprising a support according to the invention may be in extruded form, in the form of a coating having catalytic properties and based on rare earth oxide or mixture of rare earth oxides and optionally a binder. of known type on a substrate of metal or ceramic monolithic type.
• the extruded form advantageously makes it possible to shape the process of the invention in a continuous manner, which is not possible with a powder catalyst which would obstruct the various elements of the reactor.
• the term "catalytic extruded system” is understood to mean any catalytic system obtained by ejection under pressure of a paste through nozzles or dies of chosen shapes.
• the catalytic systems thus obtained may have various shapes, for example they may have cylindrical or semi-cylindrical, square, polygonal or even lobed sections, such as trilobes.
• the catalytic systems can be solid or hollow, they can have the form of monolith or honeycomb.
• inert support a support which does not come into play, as a catalyst or as a reagent, in the transcarbonation reaction of the invention and whatever either the pH. Typically, the support is neutral, that is to say that it does not substantially modify the catalytic activity of the catalytic entity.
• the support may also be described as inactive insofar as it does not exhibit any catalytic activity for the reaction and does not modify the catalytic activity of the catalytic entity.
• the supports are chosen from extrudable and non-hydrolyzable supports or monolytic and non-hydrolyzable supports.
• the support may be chosen from extrudable and non-hydrolyzable metal oxides, clays, activated carbons (blacks), ceramic or metallic monoliths.
• the support may for example be selected from titanium oxides, zirconium oxides, iron oxides; aluminum oxides, especially alundrum; silica-aluminas, for example clays; activated carbons; Kieselguhr.
• the extrudable and non-hydrolyzable metal oxides mention may preferably be made of titanium oxides, zirconium oxides, iron oxides, aluminum oxides, preferably titanium oxides, zirconium oxides, neutral aluminas. More preferably, the support is chosen from titanium oxides, zirconium oxides, iron oxides, aluminum oxides, in particular neutral aluminas, active carbons, preferably titanium oxides, zirconium oxides, neutral aluminas, activated carbons.
• the amount of catalytic entity on the support can be between 0.05 to 25% by weight relative to the total mass of the catalytic system, preferably from 1 to 10% by mass. It should be noted that this value depends in particular on the nature of the support, its specific surface area, its porosity and the desired catalytic properties.
• the catalytic system may in particular have a specific surface area of at least 1 m 2 / g, preferably the specific surface area is between 1 and 150 m 2 / g, more preferably between 3 and 100 m 2 / boy Wut.
• the catalyst system can be doped with Lewis acid type metals, for example transition metals, alkaline earth metals and metalloids.
• these catalytic entities together with the dopants form solid solutions forming a unitary entity.
• These metals can be chosen from iron (Fe “and Fe '"), copper (Cu 1 and Cu “), aluminum (AlI 111 ), titanium (Ti lv ), boron (B 111 ), zinc (Zn ”) and magnesium (Mg”).
• iron (Fe “and Fe '"), copper (Cu 1 and Cu “), aluminum (AlI 111 ), titanium (Ti lv ), boron (B 111 ), zinc (Zn ”) and magnesium (Mg” Preferably these metals are selected from the group consisting of iron (Fe “and Fe 1 "), copper (Cu 'and Cu “), titanium (Ti lv ) and zinc (Zn ").
• the relative percentage of metal relative to the catalyst may be between 0.01 and 10% by weight, preferably between 1 and 10% by weight, for example between 1 and 5% by weight.
• the catalyst systems of the invention are water-stable.
• the catalysts of the invention may contain less than 5% water. This advantageously makes it possible to carry out the transcarbonation reaction in a medium containing water, for example in a medium containing less than 15% water, for example less than 5% water.
• a medium containing water for example in a medium containing less than 15% water, for example less than 5% water.
• the catalyst according to the invention may, advantageously, be easily recovered after reaction by any method known to those skilled in the art, in particular by decantation or filtration.
• the process according to the invention is carried out at atmospheric pressure or autogenous pressure.
• autogenous pressure is meant the pressure inside the reactor which is due to the reagents used.
• autogenous pressure is understood to mean a pressure of less than 1 MPa, preferably less than 0.5 MPa, preferably less than 0.3 MPa, for example less than 0.2 MPa.
• the method according to the invention is implemented at a temperature between 25 and 250 ° C, preferably between 25 and 200 ° C, for example between 50 and 125 ⁇ €.
• the molar ratio polyol / alkyl carbonate or polyol / alkylene carbonate is between 1/6 and 1/1, preferably between 1/4 and 1/1, for example between 1/3 and 1 / 1.
• the amount of catalyst is between 0.01 and 50% by weight relative to the weight of polyol, preferably between 1 and 25% by weight, preferably between 3 and 15% by weight.
• the process according to the invention makes it possible to obtain the compound of formula (I) with good yields and a selectivity greater than 90%, even up to 99%.
• the process according to the invention is carried out in the absence of a solvent.
• the polyol may serve as a solvent for the reaction according to the invention.
• the method according to the invention can be implemented continuously or discontinuously.
• the process according to the invention is carried out continuously.
• the process may comprise a preliminary step of preparing the alkyl carbonate or the alkylene carbonate.
• This preliminary step is carried out by reaction between an alcohol or mixture of alcohols or a diol and C0 2 , in the presence of a catalytic system consisting of a catalytic entity selected from rare earth oxides and mixtures of oxides of rare earths and possibly a support.
• the catalytic entity and the support are as defined for the transcarbonation process according to the invention.
• the molar ratio between alcohol or diol and CO 2 is between 1 and 150 equivalents in moles, preferably between 1 and 100 equivalents.
• the preliminary step of preparation of the alkyl carbonate or alkylene carbonate is carried out at autogenous pressure or at atmospheric pressure.
• the preliminary step of preparing the alkyl carbonate or the alkylene carbonate is carried out at a temperature of between 25 and 250 ° C., preferably between 25 and 200 ° C., for example between 50 ° C. and 250 ° C. and 150 ° C.
• the amount of catalyst system is between 0.01 and 50% by weight relative to the weight of alcohol, mixture of alcohols or diol, preferably between 1 and 25% by weight, preferably between 3 and 15% by mass.
• the alcohol corresponds to the formula R 12 OH in which R 12 represents:
• alkyl group linear or branched, in d to C 20 ;
• a C 5 to C 14 aryl group optionally substituted in particular with a C 1 to C 9 , preferably C 1 to C 5 , alkyl group; a C 5 to C 14 , preferably C 6 to C 14 , preferably C 6 to C 10 , aryl group which is optionally substituted; an alkyl-aryl group of the formula -Q 9 -Ar 9 in which Q 9 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 9 represents a C 6 -C 14 aryl group, preferably C 6 , optionally substituted; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group at d 0, preferably -C 5; alkoxy -C 9, preferably - cycloalkyl, C 5 -C 6 alkyl optionally substituted, especially by alkyl of -C 9, preferably C 5
• heteroaryl group preferably comprising 5 to 10 members optionally substituted, in particular with a C 1 to C 9 alkyl group, preferably
• alkyl-aryl group of formula -Q 12 -Ar 12 in which Q 12 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 12 represents a C 6 -C 14 aryl group, preferably at C 6 , optionally substituted.
• R 12 represents:
• - a linear or branched alkyl group, d to C 10 , for example, methyl, ethyl, propyl, butyl;
• a C 6 , C 10 or C 14 aryl group optionally substituted in particular with a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of the formula -Q 9 -Ar 9 in which Q 9 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 9 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 is alkyl to C 10, preferably C l -C 5; alkoxy Ci to C 5, for example methoxy, ethoxy;
• a C 5 to C 6 cycloalkyl group optionally substituted, in particular with a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of the formula -Q 10 -Ar 10 in which Q 10 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 10 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group Ci-Ci 0, preferably C l -C 5; a C 5 to C 5 alkoxy group, for example methoxy, ethoxy; or
• a heteroaryl group of aniline type optionally substituted in particular with a C 1 to C 5 alkyl group, for example methyl or ethyl; an optionally substituted phenyl group; an alkyl-aryl group of formula -Q 11 -Ar 11 in which Q 11 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 11 represents an optionally substituted phenyl group, preferably methylphenyl or ethylphenyl; a polyalkoxy group having the formula - (OCH 2 CH 2) n OR 15 wherein n is an integer between 2 and 5 and R 15 represents an alkyl group of C 10, preferably C 5 d; a C 5 to C 5 alkoxy group, for example methoxy, ethoxy; an alkyl-aryl group of formula -Q 12 -Ar 12 in which Q 12 represents a C 1 -C 9 , preferably C 1 -C 5, alkyl residue and Ar 12 represents
• R 6 , R 7 , R 8 and R 9 identical or different are as defined above.
• the n and R 15 are independently selected from one another and may be the same or different.
• the catalytic system may be the same or different in the prior stage and in the transcarbonation stage.
• the catalytic system is the same in the prior stage and in the carbonation stage.
• the preliminary step and the transcarbonation step of the process according to the invention are carried out in a single sequence, continuously.
• the catalyst system may be identical or different in the previous step and in the transcarbonation step, advantageously the catalytic system is identical for both reactions.
• the process according to the invention is carried out in the absence of a solvent.
• continuous process is meant a process in which the reactants are continuously fed into the reactor and the products are withdrawn from the reaction medium continuously and then separated. The unreacted reagents can be reintroduced into the reaction medium or removed.
• the continuous process is carried out with short residence times of the reactants in the reactor.
• short residence time is meant periods of between 1 and 24 hours, preferably between 1 and 5 hours.
• the yields are molar yields of glycerol carbonate relative to the molar amount of glycerol starting.
• the yields are determined by gas chromatography using a STABILWAX® capillary column (polar phase, crossbond carbowax polyethylene glycol). Tetraethylene glycol (99%, ALFA) is used as an internal standard.
• Glycerol > 99%, SIGMA-ALDRICH), ethylene carbonate (> 99%, ACROS) and dimethyl carbonate (99%, ALFA) are commercial products.
• the process according to the invention implemented with an ethylene carbonate / glycerol ratio of 1/1, makes it possible to prepare glycerol carbonate with good yield as well as good selectivity.
• Example 1 A series of glycerol carbonate synthesis tests is carried out as described in Example 1 in which the glycerol and the ethylene carbonate are mixed according to the molar ratios indicated in Table 1.
• the process according to the invention implemented with an ethylene carbonate / glycerol ratio of between 1/1 and 3/1, makes it possible to prepare glycerol carbonate with a good yield and a good selectivity.
• the process according to the invention makes it possible to prepare glycerol carbonate with a good yield and above all a good selectivity.
• the reduction of the amount of catalyst makes it possible to maintain a good yield and a good selectivity.
• the process according to the invention makes it possible to prepare glycerol carbonate with good yield and especially good selectivity, even with greatly reduced reaction times.
• G Dimethyl carbonate (DMC) Glycerol carbonate (GC)
• the process according to the invention makes it possible to prepare glycerol carbonate with good selectivity.
• the process according to the invention makes it possible to prepare glycerol carbonate with a good yield and above all a good selectivity.
• Example 8 Catalyst Variation A series of glycerol carbonate synthesis tests is carried out as described in Example 6 but using other catalysts. The results are listed in Table 7.
• the process according to the invention makes it possible to prepare glycerol carbonate with a good yield and a good selectivity for different catalysts.
• DMC Glycerol dimethyl carbonate
• the yield is very low compared to the yield obtained with the process according to the invention.

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