EP3325458A1 - Method for producing 5-(hydroxymethyl)furfural in the presence of organic catalysts of the thiourea family - Google Patents

Method for producing 5-(hydroxymethyl)furfural in the presence of organic catalysts of the thiourea family

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Publication number
EP3325458A1
EP3325458A1 EP16741608.0A EP16741608A EP3325458A1 EP 3325458 A1 EP3325458 A1 EP 3325458A1 EP 16741608 A EP16741608 A EP 16741608A EP 3325458 A1 EP3325458 A1 EP 3325458A1
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EP
European Patent Office
Prior art keywords
groups
chosen
process according
cyclic
solvent
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EP16741608.0A
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German (de)
French (fr)
Inventor
Myriam SOULEYMANOU
Damien Delcroix
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • C07D307/38—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
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C07D307/50—Preparation from natural products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • 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
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

Definitions

  • the invention relates to a process for converting sugars and in particular hexoses to 5-hydroxymethylfurfural in the presence of new organic catalysts of the family of thioureas of low acidity and non-corrosive.
  • 5-hydroxymethylfurfural is a compound derived from biomass that can be used in many fields as precursors of active ingredients in pharmacy, agrochemicals or specialty chemicals. His interest in recent years is in its use as a precursor of furanedicarboxylic acid (FDCA) which is used as a substitute for terephthalic acid as a monomer for the production of polyester fibers or convenience plastics.
  • FDCA furanedicarboxylic acid
  • the high acidity of each of these catalysts can be characterized by the numerical value of its pKa in a solvent.
  • the pKa of the sulfuric and sulfonic acids are between 0 and 3.
  • the pKa of the sulfuric and sulfonic acids are between -14 and -2.
  • the invention therefore relates to a process for producing 5-hydroxymethylfurfural from sugars using organic catalysts based on thiourea family compounds, low acid and non-corrosive.
  • organic catalyst is meant a molecule acting as a catalyst and containing exclusively non-metallic atoms selected for example from carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur, silicon, fluorine, bromine, chlorine and iodine.
  • An advantage of the present invention is to provide a process for converting sugars to 5-hydroxymethylfurfural using one or more organic catalysts of the thiourea family, said catalysts having a low acidity, being non-corrosive and being easily recyclable.
  • the filler treated in the process according to the invention is a filler comprising at least one sugar, preferably chosen from oligosaccharides and monosaccharides, alone or as a mixture.
  • sugar is meant any oligosaccharide or monosaccharide soluble in the reaction conditions contemplated by the invention.
  • Monosaccharide more particularly denotes carbohydrates of general formula C 6 (H 2 O) 6 or C 6 H 12 0 6 .
  • the preferred monosaccharides used as filler in the present invention are selected from glucose, mannose, fructose, alone or as a mixture.
  • Oligosaccharide more particularly denotes a carbohydrate having the formula wherein n is an integer greater than 1, the monosaccharide units making up said oligosaccharide being identical or different, and / or a carbohydrate having the formula (0 6 ⁇ 1 ⁇ ⁇ + 2 ⁇ 5 ⁇ + ⁇ ) ( ⁇ 5 ⁇ 8 ⁇ + 2 ⁇ 4 ⁇ + ⁇ ) where m and n are integers greater than or equal to 1, the monosaccharide units making up said oligosaccharide being identical or different.
  • the oligosaccharides are preferably chosen from oligomers of hexoses or pentoses and of hexoses, preferably from hexose oligomers, preferably with a degree of polymerization allowing them to be soluble in the reaction conditions envisaged by the invention. They can be obtained by partial hydrolysis of polysaccharides derived from renewable resources such as starch, inulin, cellulose or hemicellulose, possibly derived from lignocellulosic biomass. For example, the steam explosion of lignocellulosic biomass is a process of partial hydrolysis of cellulose and hemicellulose contained in lignocellulosic biomass producing a flux of oligo- and monosaccharides.
  • the preferred oligosaccharides used as filler in the present invention are preferably selected from sucrose, lactose, maltose, isomaltose, inulobiosis, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose and oligosaccharides resulting from the hydrolysis of said polysaccharides resulting from the hydrolysis of starch, inulin, cellulose or hemicellulose, taken alone or as a mixture.
  • the filler comprising at least one sugar used in the process according to the invention is chosen from cellobiose, fructose and glucose, taken alone or as a mixture.
  • said filler is chosen from fructose and glucose, taken alone or as a mixture.
  • said feedstock is contacted in the process according to the invention with at least one organic catalyst of the thiourea family in the presence of at least one solvent, said solvent being water or an organic solvent , alone or a mixture, at a temperature between 30 ° C and 200 ° C, and at a pressure between 0.1 MPa and 10 MPa.
  • the groups R 1 and R 2 can be independently selected from the families of groups. For example, R 1 may be chosen from aromatic groups and R 2 from cycloalkyl groups.
  • R1 and R2 are chosen from the same grouping family, R1 and R2 may be identical or different.
  • said groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom or not and alkyl, cyclic or non-cyclic groups, said groups R 1 and R 2 may be substituted or not and identical or different and, preferably, said groups R1 and R2 are chosen from aromatic groups that do not comprise heteroatoms.
  • said groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom
  • said heteroatom is preferably chosen from nitrogen, phosphorus and oxygen.
  • said groups R1 and R2 are preferably chosen from pyridine, phosphole and furan groups.
  • said groups R 1 and R 2 are chosen from aromatic groups containing no heteroatom, they are advantageously chosen from aromatic groups having from 6 to 14 carbon atoms, fused or otherwise.
  • the aromatic groups having from 6 to 14 carbon atoms are chosen from phenyl, naphthyl, phenanthryl and anthryl groups and very preferably, said group is phenyl.
  • R 1 and R 2 groups are chosen from linear or branched, cyclic or non-cyclic alkyl groups, they are advantageously chosen from alkyl groups having from 1 to 12 carbon atoms, and preferably having from 1 to 6 atoms. carbons, and cycloalkyl groups having 3 to 8 carbon atoms, and preferably having 5 to 8 carbon atoms.
  • the non-cyclic alkyl groups having 1 to 12 carbon atoms, and preferably 1 to 6 linear or branched carbon atoms are chosen from methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl groups.
  • the cycloalkyl groups having from 3 to 8 carbon atoms and preferably having from 5 to 8 carbon atoms are chosen from cyclopentyl, cyclohexyl, cycloheptyl and bicyclo [2.2.2] octyl groups.
  • said groups R1 and R2 are chosen from alkyl groups comprising at least one heteroatom, cyclic or otherwise, said heteroatom is preferably chosen from nitrogen.
  • Said groups are therefore advantageously chosen from alkyl and / or cycloalkyl groups which may comprise at least one tertiary amine function.
  • they are advantageously chosen from N, N-dimethylethylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine and aza-bicyclo [2.2.2] octyl.
  • said groups R1 and R2 are substituted, they are preferably substituted with at least one group chosen from halogens, the groups -CX 3 with X being a halogen and preferably Fluorine, the nitro group - N0 2 , the -NHCOCH 3 group, the alkoxy groups, preferably chosen from methoxy and ethoxy groups and alkyl groups having 1 to 12 carbon atoms, linear or branched, preferably chosen from methyl, ethyl and propyl groups, butyl, pentyl and hexyl.
  • said groups R1 and R2 are substituted with at least one group chosen from halogens, the groups -CX 3 with X being a halogen and preferably Fluorine and alkoxy groups, preferably the methoxy group.
  • Said groups R1 and R2 may advantageously be mono- or disubstituted.
  • thiourea 1 thiourea 2 In the DMSO, the pKa organic catalysts of the thiourea family are between 8 and 22. They are therefore much less acidic than the strong acids conventionally used for the dehydration of sugars, such as sulfuric acid or sulfuric acid. sulfonic acids whose pKa in DMSO are between 0 and 3. These acidity ranking data are from the literature and well known to those skilled in the art, for example reference may be made to the article of FG Bordwell et al. (J. Am Chem Soc, 1991, 13, 8398-8401). Process of transformation
  • the process for transforming the feedstock comprising at least one sugar is carried out in a reaction enclosure in the presence of at least one solvent, said solvent being water or an organic solvent, alone or in mixing, at a temperature between 30 ° C and 200 ° C, and at a pressure between 0.1 MPa and 10 MPa.
  • the process is therefore carried out in a reaction vessel comprising at least one solvent and wherein said feedstock is placed in the presence of at least one organic catalyst of the thiourea family according to the invention.
  • the process operates in the presence of at least one solvent, said solvent being water or an organic solvent, alone or as a mixture.
  • the organic solvents are advantageously chosen from alcohols such as methanol, ethanol, propanols, butanols, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, esters such as ethyl formate and acetate.
  • alcohols such as methanol, ethanol, propanols, butanols, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, esters such as ethyl formate and acetate.
  • ethyl lactones such as ⁇ -valerolactone, ⁇ -butyrolactone, cyclic carbonates such as ethylene carbonate, propylene carbonate, nitriles such as acetonitrile, benzonitrile, amides such as dimethylformamide, diethylformamide, / V-methylpyrrolidone, sulfones such as dimethylsulfone, sulfolane, sulfoxides such as DMSO, ammonium salts such as choline chloride, alone or in admixture.
  • the process according to the invention operates solely in the presence of organic solvent.
  • said process according to the invention operates at a temperature between 50 ° C and 200 ° C and preferably between 50 ° C and 175 ° C, and at a pressure between 0.1 MPa and 8 MPa and preferred way between 0.1 and 5 MPa.
  • the method can be operated according to different embodiments.
  • the process can advantageously be implemented batchwise or continuously. It can be carried out in a closed reaction chamber or in a semi-open reactor.
  • the organic catalyst (s) of the thiourea family are introduced into the reaction chamber in an amount corresponding to a mass ratio of filler / organic catalyst (s) of between 1 and 1000, preferably between 1 and 500. preferably between 1 and 100, preferably between 1 and 50.
  • the filler is introduced into the process in an amount corresponding to a mass ratio solvent / filler of between 0.1 and 200, preferably between 0.3 and 100 and more preferably between 1 and 50.
  • the hourly mass velocity (mass feed rate / mass of organic catalyst (s)) is between 0.01 hr -1 and 5 hr -1 , preferably between 0 and 02 h "1 and 2 h" 1.
  • the catalyst can be easily recovered by precipitation, distillation, extraction or washing. It can also be recovered by passage over an ion exchange resin such as Amberlyst 15 or Amberlyst 31 and recycled after washing of this resin.
  • an ion exchange resin such as Amberlyst 15 or Amberlyst 31 and recycled after washing of this resin.
  • the products obtained and their mode of analysis The product of the reaction of the transformation process according to the invention is 5-hydroxymethylfurfural.
  • reaction medium is analyzed by gas phase chromatography (GC) to determine the content of 5-HMF in the presence of an internal standard and by ion chromatography to determine the conversion of the charge in the presence of an external standard.
  • GC gas phase chromatography
  • Figure 1 is a graph showing the evolution of the yield of the 5-HMF reaction from a sugar charge under different catalytic conditions.
  • glucose and fructose used as feed are commercial and used without further purification.
  • 3,5-Trifluoromethylphenyl isothiocyanate, phenyl isothiocyanate, cyclohexylamine and p-anisidine used as precursors for the catalysts according to the invention are commercial and used without further purification.
  • N-methylpyrrolidone, NMP in the examples, used as a solvent is commercial and used without further purification.
  • the molar yield of thiourea is calculated by the ratio between the number of moles of thiourea obtained and the number of moles of isothiocyanate reagent involved.
  • the molar yield of 5-HMF is calculated by the ratio of the number of moles of 5-HMF obtained to the number of moles of sugar filler engaged.
  • the catalyst of Example 2 (0.044 g, 0.17 mmol) was added to a solution of fructose (2.0 g, 1 1, 10 mmol) in NMP (20 g).
  • the mass ratio filler / catalyst is 45.5.
  • the solvent / filler mass ratio is 10.
  • the reaction medium is then stirred at 120 ° C. for 6 h.
  • the conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography.
  • the molar yield of 5-HMF after 6h is 59%.
  • the catalyst of Example 1 (0.046 g, 0.12 mmol) was added to a mixture of fructose and glucose 50% w / wt% (2.0 g, 1 1, 10 mmol) in NMP (20 mmol). boy Wut).
  • the mass ratio filler / catalyst is 43.5.
  • the solvent / filler mass ratio is 10.
  • the reaction medium is then stirred at 120 ° C. for 6 h.
  • the conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography.
  • the molar yield of 5-HMF after 6h is 58%.
  • the catalyst of Example 2 (0.044 g, 0.17 mmol) is added to a mixture of fructose and glucose 50% w / wt% (2.0 g, 1 1, 10 mmol) in NMP (20 mg / ml). boy Wut).
  • the mass ratio filler / catalyst is 45.5.
  • the solvent / filler mass ratio is 10.
  • the reaction medium is then stirred at 120 ° C. for 6 h.
  • the conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography.
  • the molar yield of 5-HMF after 6 hours is 60%. Comparative Example 7 Transformation of fructose without catalyst (non-compliant)
  • the kinetics of reaction is faster and the yield of 5-HMF is greater in the case of the use of weakly organic organic catalysts of the thiourea family according to the invention compared to a strong sulfonic acid such as Amberlyst 15, namely about 60% molar yield of 5-HMF in the presence of thiourea against 45% for the acidic resin Amberlyst 15 after 6 hours of reaction.
  • a strong sulfonic acid such as Amberlyst 15, namely about 60% molar yield of 5-HMF in the presence of thiourea against 45% for the acidic resin Amberlyst 15 after 6 hours of reaction.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Saccharide Compounds (AREA)
  • Catalysts (AREA)
  • Furan Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention relates to a new method for transforming feedstock comprising at least one sugar into 5-(hydroxymethyl)furfural, in which method the feedstock is brought into contact with one or more organic catalysts in the presence of at least one solvent, which is water or an organic solvent, either alone or in combination, at a temperature ranging from 30°C to 200°C, and under a pressure ranging from 0.1 MPa to 10 MPa, the organic catalysts being selected from compounds of the thiourea family and having the general formula R1NH-C(=S)-NHR2, in which the R1 and R2 groups are selected from aromatic compounds optionally comprising a heteroatom, from linear or branched, cyclic or non-cyclic alkyl groups, and from linear or branched, cyclic or non-cyclic alkyl groups comprising at least one heteroatom, said R1 and R2 groups being optionally substituted and the same or different.

Description

PROCEDE DE PRODUCTION DE 5-HYDROXYMETHYLFURFURAL EN PRESENCE DE CATALYSEURS ORGANIQUES DE LA FAMILLE DES THIOUREES  PROCESS FOR THE PRODUCTION OF 5-HYDROXYMETHYLFURFURAL IN THE PRESENCE OF ORGANIC CATALYSTS OF THE THIOURE FAMILY
Domaine technique de l'invention Technical field of the invention
L'invention concerne un procédé de transformation de sucres et en particulier les hexoses en 5-hydroxyméthylfurfural en présence de nouveaux catalyseurs organiques de la famille des thiourées de faible acidité et non corrosifs. The invention relates to a process for converting sugars and in particular hexoses to 5-hydroxymethylfurfural in the presence of new organic catalysts of the family of thioureas of low acidity and non-corrosive.
Art antérieur Prior art
Le 5-hydroxyméthylfurfural (5-HMF) est un composé dérivé de la biomasse qui peut être valorisé dans de nombreux domaines comme précurseurs de principes actifs en pharmacie, en agrochimie ou en chimie de spécialité. Son intérêt réside ces dernières années dans son utilisation comme précurseur de l'acide furanedicarboxylique (FDCA) qui est utilisé comme substitut à l'acide téréphthalique en tant que monomère pour la production de fibres polyesters ou de plastiques de commodité. 5-hydroxymethylfurfural (5-HMF) is a compound derived from biomass that can be used in many fields as precursors of active ingredients in pharmacy, agrochemicals or specialty chemicals. His interest in recent years is in its use as a precursor of furanedicarboxylic acid (FDCA) which is used as a substitute for terephthalic acid as a monomer for the production of polyester fibers or convenience plastics.
La production de 5-HMF par déshydratation d'hexoses est connue depuis de nombreuses années et a fait l'objet d'un nombre important de travaux de recherches. La déshydratation du glucose ou du fructose en 5-HMF est très majoritairement décrite avec des catalyseurs acides forts de Bronsted ou de Lewis. L'article de Horvath et al. (ACS Catal. 2014, 4, 1470-1477) décrit par exemple la transformation de sucres en présence d'acide sulfurique dans la γ-valérolactone. Des acides sulfoniques hétérogènes comme les résines Amberlyst sont également largement utilisées pour la transformation de fructose en 5-HMF comme détaillé dans l'article de Schuth et al. (ACS Catal. 2013, 3, 123-127). The production of 5-HMF by dehydration of hexoses has been known for many years and has been the subject of a large number of research projects. The dehydration of glucose or fructose to 5-HMF is very predominantly described with strong Bronsted or Lewis acid catalysts. The article by Horvath et al. (ACS Catal 2014, 4, 1470-1477) describes, for example, the transformation of sugars in the presence of sulfuric acid in γ-valerolactone. Heterogeneous sulfonic acids such as Amberlyst resins are also widely used for the conversion of fructose to 5-HMF as detailed in the article by Schuth et al. (ACS Catal 2013, 3, 123-127).
Tous ces composés sont des acides forts et corrosifs ainsi que toxiques pour la plupart, dont l'élimination et le recyclage sont difficiles et peuvent engendrer des problèmes environnementaux. All of these compounds are strong and corrosive acids, and most of them are toxic, the disposal and recycling of which are difficult and can lead to environmental problems.
La forte acidité de chacun de ces catalyseurs peut être caractérisée par la valeur numérique de son pKa dans un solvant. Par exemple, dans le DMSO, les pKa des acides sulfuriques et sulfoniques sont compris entre 0 et 3. Par exemple, dans l'eau, les pKa des acides sulfuriques et sulfoniques sont compris entre -14 et -2. Ces données de classement d'acidité sont issues de la littérature et bien connues de l'homme de l'art, par exemple on peut se référer à l'article de F. G. Bordwell et al. (J. Am. Chem. Soc, 1991 , 1 13, 8398-8401 ). The high acidity of each of these catalysts can be characterized by the numerical value of its pKa in a solvent. For example, in the DMSO, the pKa of the sulfuric and sulfonic acids are between 0 and 3. For example, in water, the pKa of the sulfuric and sulfonic acids are between -14 and -2. These acidity ranking data are from the literature and well known to those skilled in the art, for example reference can be made to the article by F. G. Bordwell et al. (J. Am Chem Soc, 1991, 13, 8398-8401).
Il existe donc un besoin de développement de nouveaux procédés utilisant des systèmes catalytiques moins acides et moins corrosifs. L'invention concerne donc un procédé de production de 5- hydroxyméthylfurfural à partir de sucres utilisant des catalyseurs organiques à base de composés de la famille des thiourées, peu acides et non corrosifs. Objet de l'invention There is therefore a need for the development of new processes using catalytic systems that are less acidic and less corrosive. The invention therefore relates to a process for producing 5-hydroxymethylfurfural from sugars using organic catalysts based on thiourea family compounds, low acid and non-corrosive. Object of the invention
Un objet de la présente invention est donc de fournir un nouveau procédé de transformation d'une charge comprenant au moins un sucre en 5-hydroxyméthylfurfural, dans lequel ladite charge est mise en contact avec un ou plusieurs catalyseurs organiques en présence d'au moins un solvant, ledit solvant étant l'eau ou un solvant organique seuls ou en mélange, à une température comprise entre 30°C et 200°C, et à une pression comprise entre 0,1 MPa et 10 MPa dans lequel lesdits catalyseurs organiques sont choisis parmi les composés de la famille des thiourées de formule générale R1 NH-C(=S)-NHR2 dans laquelle les groupements R1 et R2 sont choisis parmi les groupements aromatiques comprenant un hétéroatome ou non, les groupements alkyles linéaires ou ramifiés, cycliques ou non cycliques, et les groupements alkyles comportant au moins un hétéroatome, linéaires ou ramifiés, cycliques ou non cycliques, lesdits groupements R1 et R2 pouvant être substitués ou non et identiques ou différents. An object of the present invention is therefore to provide a new process for transforming a feedstock comprising at least one 5-hydroxymethylfurfural sugar, wherein said feedstock is contacted with one or more organic catalysts in the presence of at least one solvent, said solvent being water or an organic solvent alone or as a mixture, at a temperature between 30 ° C and 200 ° C, and at a pressure of between 0.1 MPa and 10 MPa wherein said organic catalysts are chosen among the compounds of the family of thioureas of general formula R 1 NH-C (= S) -NHR 2 in which the groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom or not, linear or branched alkyl groups, cyclic or otherwise cyclic, and alkyl groups containing at least one heteroatom, linear or branched, cyclic or non-cyclic, said groups R1 and R2 may be substituted or not and identi different.
On entend par catalyseur organique, une molécule jouant le rôle de catalyseur et contenant exclusivement des atomes non-métalliques choisis par exemple parmi le carbone, l'hydrogène, l'oxygène, l'azote, le phosphore, le soufre, le silicium, le fluor, le brome, le chlore et l'iode. By organic catalyst is meant a molecule acting as a catalyst and containing exclusively non-metallic atoms selected for example from carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur, silicon, fluorine, bromine, chlorine and iodine.
Un avantage de la présente invention est de fournir un procédé de transformation de sucres en 5-hydroxyméthylfurfural utilisant un ou plusieurs catalyseurs organiques de la famille des thiourées, lesdits catalyseurs présentant une faible acidité, étant non-corrosifs et étant facilement recyclables. An advantage of the present invention is to provide a process for converting sugars to 5-hydroxymethylfurfural using one or more organic catalysts of the thiourea family, said catalysts having a low acidity, being non-corrosive and being easily recyclable.
Description détaillée de l'invention La charge Detailed Description of the Invention The Charge
Conformément à l'invention, la charge traitée dans le procédé selon l'invention est une charge comprenant au moins un sucre, de préférence choisis parmi les oligosaccharides et les monosaccharides, seuls ou en mélange. According to the invention, the filler treated in the process according to the invention is a filler comprising at least one sugar, preferably chosen from oligosaccharides and monosaccharides, alone or as a mixture.
Par sucre, on entend tout oligosaccharide ou monosaccharide soluble dans les conditions réactionnelles envisagées par l'invention. By sugar is meant any oligosaccharide or monosaccharide soluble in the reaction conditions contemplated by the invention.
Par monosaccharide, on désigne plus particulièrement les hydrates de carbone de formule générale C6(H20)6 ou C6H1206. Les monosaccharides préférés utilisés comme charge dans la présente invention sont choisis parmi le glucose, le mannose, le fructose, pris seuls ou en mélange. Monosaccharide more particularly denotes carbohydrates of general formula C 6 (H 2 O) 6 or C 6 H 12 0 6 . The preferred monosaccharides used as filler in the present invention are selected from glucose, mannose, fructose, alone or as a mixture.
Par oligosaccharide, on désigne plus particulièrement un hydrate de carbone ayant pour formule brute où n est un entier supérieur à 1 , les unités monosaccharidiques composant ledit oligosaccharide étant identiques ou non, et/ou un hydrate de carbone ayant pour formule brute (06πΗ1 θΓτι+2θ5Γτι+ι )(θ5ηΗ8η+2θ4η+ι ) où m et n sont des entiers supérieurs ou égaux à 1 , les unités monosaccharidiques composant ledit oligosaccharide étant identiques ou non. Oligosaccharide more particularly denotes a carbohydrate having the formula wherein n is an integer greater than 1, the monosaccharide units making up said oligosaccharide being identical or different, and / or a carbohydrate having the formula (0 6 πΗ 1 θΓ τι + 2θ5Γτι + ι) (θ5ηΗ8η + 2θ4η + ι) where m and n are integers greater than or equal to 1, the monosaccharide units making up said oligosaccharide being identical or different.
Les oligosaccharides sont de préférence choisis parmi les oligomères d'hexoses ou de pentoses et d'hexoses, de préférence parmi les oligomères d'hexoses, de préférence avec un degré de polymérisation leur permettant d'être soluble dans les conditions réactionnelles envisagées par l'invention. Ils peuvent être obtenus par hydrolyse partielle de polysaccharides issus de ressources renouvelables tels que l'amidon, l'inuline, la cellulose ou l'hémicellulose, éventuellement issus de la biomasse lignocellulosique. Par exemple, l'explosion à la vapeur de la biomasse lignocellulosique est un procédé d'hydrolyse partielle de la cellulose et de l'hémicellulose contenues dans la biomasse lignocellulosique produisant un flux d'oligo- et monosaccharides. The oligosaccharides are preferably chosen from oligomers of hexoses or pentoses and of hexoses, preferably from hexose oligomers, preferably with a degree of polymerization allowing them to be soluble in the reaction conditions envisaged by the invention. They can be obtained by partial hydrolysis of polysaccharides derived from renewable resources such as starch, inulin, cellulose or hemicellulose, possibly derived from lignocellulosic biomass. For example, the steam explosion of lignocellulosic biomass is a process of partial hydrolysis of cellulose and hemicellulose contained in lignocellulosic biomass producing a flux of oligo- and monosaccharides.
Les oligosaccharides préférés utilisés comme charge dans la présente invention sont de préférence choisis parmi le saccharose, le lactose, le maltose, l'isomaltose, l'inulobiose, le mélibiose, le gentiobiose, le tréhalose, le cellobiose, le cellotriose, le cellotetraose et les oligosaccharides issus de l'hydrolyse desdits polysaccharides issus de l'hydrolyse de l'amidon, de l'inuline, de la cellulose ou de l'hémicellulose, pris seuls ou en mélange. The preferred oligosaccharides used as filler in the present invention are preferably selected from sucrose, lactose, maltose, isomaltose, inulobiosis, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose and oligosaccharides resulting from the hydrolysis of said polysaccharides resulting from the hydrolysis of starch, inulin, cellulose or hemicellulose, taken alone or as a mixture.
De préférence, la charge comprenant au moins un sucre utilisée dans le procédé selon l'invention est choisie parmi le cellobiose, le fructose et le glucose, pris seuls ou en mélange. Preferably, the filler comprising at least one sugar used in the process according to the invention is chosen from cellobiose, fructose and glucose, taken alone or as a mixture.
De manière très préférée, ladite charge est choisie parmi le fructose et le glucose, pris seuls ou en mélange. Les catalyseurs Very preferably, said filler is chosen from fructose and glucose, taken alone or as a mixture. Catalysts
Conformément à l'invention, ladite charge est mise en contact dans le procédé selon l'invention, avec au moins un catalyseur organique de la famille des thiourées en présence d'au moins un solvant, ledit solvant étant l'eau ou un solvant organique, seuls ou un mélange, à une température comprise entre 30°C et 200°C, et à une pression comprise entre 0,1 MPa et 10 MPa. Conformément à l'invention, le catalyseur est choisi parmi les composés de la famille des thiourées de formule générale R1 NH-C(=S)-NHR2 dans laquelle les groupements R1 et R2 sont choisis parmi les groupements aromatiques comprenant un hétéroatome ou non, les groupements alkyles linéaires ou ramifiées, cycliques ou non cycliques, et les groupements alkyles comportant au moins un hétéroatome, linéaires ou ramifiés, cycliques ou non cycliques, lesdits groupements R1 et R2 pouvant être substitués ou non et identiques ou différents. Les groupements R1 et R2 peuvent être indépendamment choisis parmi les familles de groupements. Par exemple R1 peut-être choisi parmi les groupements aromatiques et R2 parmi les groupements cycloalkyles. According to the invention, said feedstock is contacted in the process according to the invention with at least one organic catalyst of the thiourea family in the presence of at least one solvent, said solvent being water or an organic solvent , alone or a mixture, at a temperature between 30 ° C and 200 ° C, and at a pressure between 0.1 MPa and 10 MPa. According to the invention, the catalyst is chosen from compounds of the family of thioureas of general formula R 1 NH-C (= S) -NHR 2 in which the groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom or not, linear or branched alkyl groups, cyclic or non-cyclic, and alkyl groups containing at least one heteroatom, linear or branched, cyclic or non-cyclic, said groups R1 and R2 may be substituted or not and the same or different. The groups R 1 and R 2 can be independently selected from the families of groups. For example, R 1 may be chosen from aromatic groups and R 2 from cycloalkyl groups.
Dans le cas où R1 et R2 sont choisis dans une même famille de groupement, R1 et R2 peuvent être identiques ou différents. In the case where R1 and R2 are chosen from the same grouping family, R1 and R2 may be identical or different.
De préférence, lesdits groupements R1 et R2 sont choisis parmi les groupements aromatiques comprenant un hétéroatome ou non et les groupements alkyles, cycliques ou non cycliques, lesdits groupements R1 et R2 pouvant être substitués ou non et identiques ou différents et de manière préférée, les dits groupements R1 et R2 sont choisis parmi les groupements aromatiques ne comprenant pas d'hétéroatomes. Preferably, said groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom or not and alkyl, cyclic or non-cyclic groups, said groups R 1 and R 2 may be substituted or not and identical or different and, preferably, said groups R1 and R2 are chosen from aromatic groups that do not comprise heteroatoms.
Dans le cas où lesdits groupements R1 et R2 sont choisis parmi les groupements aromatiques comprenant un hétéroatome, ledit hétéroatome est de préférence choisi parmi l'azote, le phosphore et l'oxygène. Dans ce cas, lesdits groupements R1 et R2 sont de préférence choisis parmi les groupements pyridine, phosphole et furane. Dans le cas où lesdits groupements R1 et R2 sont choisis parmi les groupements aromatiques ne comprenant pas d'hétéroatome, ils sont avantageusement choisis parmi les groupements aromatiques ayant de 6 à 14 atomes de carbones, fusionnés ou non. In the case where said groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom, said heteroatom is preferably chosen from nitrogen, phosphorus and oxygen. In this case, said groups R1 and R2 are preferably chosen from pyridine, phosphole and furan groups. In the case where said groups R 1 and R 2 are chosen from aromatic groups containing no heteroatom, they are advantageously chosen from aromatic groups having from 6 to 14 carbon atoms, fused or otherwise.
De manière préférée, les groupements aromatiques ayant de 6 à 14 atomes de carbones sont choisis parmi les groupements phényle, naphtyle, phénanthryle et anthryle et de manière très préférée, ledit groupement est le phényle. Preferably, the aromatic groups having from 6 to 14 carbon atoms are chosen from phenyl, naphthyl, phenanthryl and anthryl groups and very preferably, said group is phenyl.
Dans le cas où lesdits groupements R1 et R2 sont choisis parmi les groupements alkyles, linéaires ou ramifiés, cycliques ou non, ils sont avantageusement choisis parmi les groupements alkyles ayant de 1 à 12 atomes de carbones, et de préférence ayant de 1 à 6 atomes de carbones, et les groupements cycloalkyles ayant de 3 à 8 atomes de carbones, et de préférence ayant de 5 à 8 atomes de carbones. In the case where said R 1 and R 2 groups are chosen from linear or branched, cyclic or non-cyclic alkyl groups, they are advantageously chosen from alkyl groups having from 1 to 12 carbon atoms, and preferably having from 1 to 6 atoms. carbons, and cycloalkyl groups having 3 to 8 carbon atoms, and preferably having 5 to 8 carbon atoms.
De préférence, les groupements alkyles non cycliques ayant de 1 à 12 atomes de carbones, et de préférence 1 à 6 atomes de carbones linéaires ou ramifiés, sont choisis parmi les groupements méthyle, éthyle, propyle, isopropyle, butyle, pentyle et hexyle. Preferably, the non-cyclic alkyl groups having 1 to 12 carbon atoms, and preferably 1 to 6 linear or branched carbon atoms, are chosen from methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl groups.
De préférence, les groupements cycloalkyles ayant de 3 à 8 atomes de carbones et de préférence ayant de 5 à 8 atomes de carbones sont choisis parmi les groupements cyclopentyle, cyclohexyle, cycloheptyle et bicyclo[2.2.2]octyle. Dans le cas où lesdits groupements R1 et R2 sont choisis parmi les groupements alkyles comportant au moins un hétéroatome, cycliques ou non, ledit hétéroatome est de préférence choisi parmi l'azote. Preferably, the cycloalkyl groups having from 3 to 8 carbon atoms and preferably having from 5 to 8 carbon atoms are chosen from cyclopentyl, cyclohexyl, cycloheptyl and bicyclo [2.2.2] octyl groups. In the case where said groups R1 and R2 are chosen from alkyl groups comprising at least one heteroatom, cyclic or otherwise, said heteroatom is preferably chosen from nitrogen.
Lesdits groupements sont donc avantageusement choisis parmi les groupements alkyles et/ou cycloalkyles pouvant comprendre au moins une fonction aminé tertiaire. Dans ce cas, ils sont avantageusement choisis parmi la A/,/V-diméthyléthylamine, la Λ/,/V-diméthylcyclohexylamine, la N- méthylpipéridine et l'aza-bicyclo[2.2.2]octyle. Said groups are therefore advantageously chosen from alkyl and / or cycloalkyl groups which may comprise at least one tertiary amine function. In this case, they are advantageously chosen from N, N-dimethylethylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine and aza-bicyclo [2.2.2] octyl.
Dans le cas où lesdits groupements R1 et R2 sont substitués, ils sont, de manière préférée, substitués par au moins un groupe choisi parmi les halogènes, les groupements -CX3 avec X étant un halogène et de préférence le Fluor, le groupement nitro -N02, le groupement -NHCOCH3, les groupements alcoxy, de préférence choisis parmi les groupes méthoxy et éthoxy et les groupements alkyle ayant 1 à 12 atomes de carbones, linéaires ou ramifiés, de préférence choisis parmi les groupements méthyle, éthyle, propyle, butyle, pentyle et hexyle. In the case where said groups R1 and R2 are substituted, they are preferably substituted with at least one group chosen from halogens, the groups -CX 3 with X being a halogen and preferably Fluorine, the nitro group - N0 2 , the -NHCOCH 3 group, the alkoxy groups, preferably chosen from methoxy and ethoxy groups and alkyl groups having 1 to 12 carbon atoms, linear or branched, preferably chosen from methyl, ethyl and propyl groups, butyl, pentyl and hexyl.
De préférence, lesdits groupements R1 et R2 sont substitués par au moins un groupe choisi parmi les halogènes, les groupements -CX3 avec X étant un halogène et de préférence le Fluor et les groupements alcoxy, de préférence le groupe méthoxy. Lesdits groupements R1 et R2 peuvent avantageusement être mono- ou disubstitués. Preferably, said groups R1 and R2 are substituted with at least one group chosen from halogens, the groups -CX 3 with X being a halogen and preferably Fluorine and alkoxy groups, preferably the methoxy group. Said groups R1 and R2 may advantageously be mono- or disubstituted.
Des catalyseurs organiques préférés sont avantageusement choisis parmi les catalyseurs organiques suivants : la 1 -(3,5-bis-trifluorométhyl-phényl)-3-cyclohexylthiourée correspondant à la formule générale nommée thiourée 1 et ayant un pKa = 10 dans le DMSO, et la 1 -(4-méthoxyphényl)-3- phénylthiourée correspondant à la formule générale nommée thiourée 2 et ayant un pKa = 14 dans le DMSO, Les appellations thiourée 1 , et thiourée 2, sont propres au texte et visent à simplifier l'écriture de ces catalyseurs organiques de la famille des thiourées dont les formules sont données ci-dessous : Preferred organic catalysts are advantageously chosen from the following organic catalysts: 1- (3,5-bis-trifluoromethyl-phenyl) -3-cyclohexylthiourea corresponding to the general formula named thiourea 1 and having a pKa = 10 in DMSO, and 1- (4-methoxyphenyl) -3-phenylthiourea corresponding to the general formula named thiourea 2 and having a pKa = 14 in DMSO, the names thiourea 1 and thiourea 2, are specific to the text and are intended to simplify the writing of these organic catalysts of the family of thioureas whose formulas are given below:
thiourée 1 thiourée 2 Dans le DMSO, les pKa des catalyseurs organiques de la famille des thiourées sont compris entre 8 et 22. Ils sont donc beaucoup moins acides que les acides forts classiquement utilisés pour la déshydratation de sucres, comme l'acide sulfurique ou les acides sulfoniques dont les pKa dans le DMSO sont compris entre 0 et 3. Ces données de classement d'acidité sont issues de la littérature et bien connues de l'homme de l'art, par exemple on peut se référer à l'article de F. G. Bordwell et al. (J. Am. Chem. Soc, 1991 , 1 13, 8398-8401 ). Procédé de transformation thiourea 1 thiourea 2 In the DMSO, the pKa organic catalysts of the thiourea family are between 8 and 22. They are therefore much less acidic than the strong acids conventionally used for the dehydration of sugars, such as sulfuric acid or sulfuric acid. sulfonic acids whose pKa in DMSO are between 0 and 3. These acidity ranking data are from the literature and well known to those skilled in the art, for example reference may be made to the article of FG Bordwell et al. (J. Am Chem Soc, 1991, 13, 8398-8401). Process of transformation
Conformément à l'invention, le procédé de transformation de la charge comprenant au moins un sucre est mis en œuvre dans une enceinte réactionnelle en présence d'au moins un solvant, ledit solvant étant de l'eau ou un solvant organique, seuls ou en mélange, à une température comprise entre 30°C et 200°C, et à une pression comprise entre 0,1 MPa et 10 MPa. According to the invention, the process for transforming the feedstock comprising at least one sugar is carried out in a reaction enclosure in the presence of at least one solvent, said solvent being water or an organic solvent, alone or in mixing, at a temperature between 30 ° C and 200 ° C, and at a pressure between 0.1 MPa and 10 MPa.
Le procédé est donc mis en œuvre dans une enceinte réactionnelle comprenant au moins un solvant et dans laquelle ladite charge est mise en présence d'au moins un catalyseur organique de la famille des thiourées selon l'invention. The process is therefore carried out in a reaction vessel comprising at least one solvent and wherein said feedstock is placed in the presence of at least one organic catalyst of the thiourea family according to the invention.
Conformément à l'invention, le procédé opère en présence d'au moins un solvant, ledit solvant étant l'eau ou un solvant organique, seuls ou en mélange. According to the invention, the process operates in the presence of at least one solvent, said solvent being water or an organic solvent, alone or as a mixture.
Les solvants organiques sont avantageusement choisis parmi les alcools comme le méthanol, l'éthanol, les propanols, les butanols, les éthers comme le diéthyléther, le diméthoxyéthane, le tétrahydrofurane, le dioxane, les esters comme le formiate d'éthyle, l'acétate d'éthyle, les lactones comme la γ-valérolactone, la γ-butyrolactone, les carbonates cycliques comme l'éthylène carbonate, le propylène carbonate, les nitriles comme l'acétonitrile, le benzonitrile, les amides comme le diméthylformamide, le diéthylformamide, la /V-méthylpyrrolidone, les sulfones comme la diméthylsulfone, le sulfolane, les sulfoxides comme le DMSO, les sels d'ammonium comme le chlorure de choline, seuls ou en mélange. The organic solvents are advantageously chosen from alcohols such as methanol, ethanol, propanols, butanols, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, esters such as ethyl formate and acetate. ethyl lactones such as γ-valerolactone, γ-butyrolactone, cyclic carbonates such as ethylene carbonate, propylene carbonate, nitriles such as acetonitrile, benzonitrile, amides such as dimethylformamide, diethylformamide, / V-methylpyrrolidone, sulfones such as dimethylsulfone, sulfolane, sulfoxides such as DMSO, ammonium salts such as choline chloride, alone or in admixture.
Selon un autre mode de réalisation, le procédé selon l'invention opère uniquement en présence de solvant organique. According to another embodiment, the process according to the invention operates solely in the presence of organic solvent.
De préférence, ledit procédé selon l'invention opère à une température comprise entre 50°C et 200°C et de manière préférée entre 50°C et 175°C, et à une pression comprise entre 0,1 MPa et 8 MPa et de manière préférée entre 0,1 et 5 MPa. Preferably, said process according to the invention operates at a temperature between 50 ° C and 200 ° C and preferably between 50 ° C and 175 ° C, and at a pressure between 0.1 MPa and 8 MPa and preferred way between 0.1 and 5 MPa.
Généralement le procédé peut être opéré selon différents modes de réalisation. Ainsi, le procédé peut avantageusement être mis en œuvre en discontinu ou en continu. On peut opérer dans une enceinte réactionnelle fermée ou en réacteur semi-ouvert. Generally the method can be operated according to different embodiments. Thus, the process can advantageously be implemented batchwise or continuously. It can be carried out in a closed reaction chamber or in a semi-open reactor.
Le ou les catalyseurs organiques de la famille des thiourées sont introduits dans l'enceinte réactionnelle à raison d'une quantité correspondant à un rapport massique charge/catalyseur(s) organique(s) compris entre 1 et 1000, de préférence entre 1 et 500, de préférence entre 1 et 100, de préférence entre 1 et 50. La charge est introduite dans le procédé à raison d'une quantité correspondant à un rapport massique solvant/charge compris entre 0,1 et 200, de préférence entre 0,3 et 100 et encore préférentiellement entre 1 et 50. The organic catalyst (s) of the thiourea family are introduced into the reaction chamber in an amount corresponding to a mass ratio of filler / organic catalyst (s) of between 1 and 1000, preferably between 1 and 500. preferably between 1 and 100, preferably between 1 and 50. The filler is introduced into the process in an amount corresponding to a mass ratio solvent / filler of between 0.1 and 200, preferably between 0.3 and 100 and more preferably between 1 and 50.
Si l'on choisit un procédé en continu, la vitesse massique horaire (débit de charge massique/masse de catalyseur(s) organique(s)) est entre 0,01 h"1 et 5 h"1 , de préférence entre 0,02 h"1 et 2 h"1. If a continuous process is chosen, the hourly mass velocity (mass feed rate / mass of organic catalyst (s)) is between 0.01 hr -1 and 5 hr -1 , preferably between 0 and 02 h "1 and 2 h" 1.
A la fin de la réaction, le catalyseur peut être facilement récupéré par précipitation, distillation, extraction ou lavage. Il peut être également récupéré par passage sur une résine échangeuse d'ion comme l'Amberlyst 15 ou l'Amberlyst 31 et recyclé après lavage de cette résine. At the end of the reaction, the catalyst can be easily recovered by precipitation, distillation, extraction or washing. It can also be recovered by passage over an ion exchange resin such as Amberlyst 15 or Amberlyst 31 and recycled after washing of this resin.
Les produits obtenus et leur mode d'analyse Le produit de la réaction du procédé de transformation selon l'invention est le 5-hydroxyméthylfurfural. The products obtained and their mode of analysis The product of the reaction of the transformation process according to the invention is 5-hydroxymethylfurfural.
A l'issue de la réaction, le milieu réactionnel est analysé par chromatographie phase gaz (GC) pour déterminer la teneur en 5-HMF en présence d'un étalon interne et par chromatographie ionique pour déterminer la conversion de la charge en présence d'un étalon externe. At the end of the reaction, the reaction medium is analyzed by gas phase chromatography (GC) to determine the content of 5-HMF in the presence of an internal standard and by ion chromatography to determine the conversion of the charge in the presence of an external standard.
Brève description des figures La figure 1 est un graphique représentant l'évolution du rendement de la réaction de production de 5- HMF à partir d'une charge sucre dans différentes conditions catalytiques. Brief Description of the Figures Figure 1 is a graph showing the evolution of the yield of the 5-HMF reaction from a sugar charge under different catalytic conditions.
EXEMPLES EXAMPLES
Dans les exemples ci-dessous, le glucose et le fructose utilisés comme charge sont commerciaux et utilisés sans purification supplémentaire. Le 3,5-trifluorométhylphényl isothiocyanate, le phényl isothiocyanate, la cyclohexylamine et la p- anisidine utilisés comme précurseurs pour les catalyseurs selon l'invention sont commerciaux et utilisés sans purification supplémentaire. In the examples below, glucose and fructose used as feed are commercial and used without further purification. 3,5-Trifluoromethylphenyl isothiocyanate, phenyl isothiocyanate, cyclohexylamine and p-anisidine used as precursors for the catalysts according to the invention are commercial and used without further purification.
L'Amberlyst 15 est commerciale et utilisée sans purification supplémentaire. Amberlyst 15 is commercial and used without further purification.
La /V-méthylpyrrolidone, notée NMP dans les exemples, utilisée comme solvant est commerciale et utilisée sans purification supplémentaire. N-methylpyrrolidone, NMP in the examples, used as a solvent is commercial and used without further purification.
Pour les exemples 1 et 2 de préparation des catalyseurs de la famille des thiourées, le rendement molaire en thiourée est calculé par le rapport entre le nombre de moles de thiourée obtenue et le nombre de moles de réactif isothiocyanate engagé. Pour les exemples 3 à 8 de transformation de sucres en 5-HMF, le rendement molaire en 5-HMF est calculé par le rapport entre le nombre de moles de 5-HMF obtenu et le nombre de moles de charge sucre engagé. For Examples 1 and 2 of the preparation of thiourea family catalysts, the molar yield of thiourea is calculated by the ratio between the number of moles of thiourea obtained and the number of moles of isothiocyanate reagent involved. For Examples 3-8 of conversion of sugars to 5-HMF, the molar yield of 5-HMF is calculated by the ratio of the number of moles of 5-HMF obtained to the number of moles of sugar filler engaged.
Exemple 1 : Préparation du catalyseur organique thiourée 1 Le 3,5-trifluorométhylphényl isothiocyanate (1 ,485 g, 5,5 mmol) et la cyclohexamine (0,595 g, 6 mmol) sont dissous dans du dichlorométhane anhydre et le milieu réactionnel est agité une nuit à température ambiante. Le solvant est ensuite évaporé sous vide et le brut obtenu est purifié par chromatographie sur colonne de silice, la phase mobile étant un gradient CH2CI2/MeOH. La masse de thiourée 1 obtenue est de 0,83 g. Le rendement molaire correspondant en thiourée 1 est de 41 % après purification. EXAMPLE 1 Preparation of Thiourea Organic Catalyst 1 3,5-trifluoromethylphenyl isothiocyanate (1.485 g, 5.5 mmol) and cyclohexamine (0.595 g, 6 mmol) are dissolved in anhydrous dichloromethane and the reaction mixture is stirred for a period of one hour. night at room temperature. The solvent is then evaporated under vacuum and the crude obtained is purified by chromatography on a silica column, the mobile phase being a CH 2 Cl 2 / MeOH gradient. The mass of thiourea 1 obtained is 0.83 g. The corresponding molar yield of thiourea 1 is 41% after purification.
Formule brute : C15H16F6N2S Masse moléculaire : 370,09 g. mol"1 Crude formula: C 15 H 16 F 6 N 2 S Molecular weight: 370.09 g. mol "1
RMN1 H (δ (ppm), (CD3)2CO, 300 MHz) 8,29 (s, 2H), 7,67 (s, 1 H), 4,35-4,15 (m, 1 H), 1 ,81 -1 ,54 (m, 4H), 1 ,45-1 ,08 (m, 6H) 1 H NMR (δ (ppm), (CD 3 ) 2 CO, 300 MHz) 8.29 (s, 2H), 7.67 (s, 1H), 4.35-4.15 (m, 1H) ), 1.81-1.54 (m, 4H), 1.45-1.08 (m, 6H)
Exemple 2 : Préparation du catalyseur organique thiourée 2 Le phényl isothiocyanate (0,564 g, 4,17 mmol) et la p-anisidine (0,510 g, 4,14 mmol) sont dissous dans du dichlorométhane anhydre et le milieu réactionnel est agité une nuit à température ambiante. Le solvant est ensuite évaporé sous vide et le brut obtenu est purifié par recristallisation dans un mélange EtOH/acétone. La masse de thiourée 2 obtenue est de 0,48 g. Le rendement molaire correspondant en thiourée 2 est de 45% après purification. Formule brute : C14H14N2OS Masse moléculaire : 258,05 g. mol"1 EXAMPLE 2 Preparation of the Thiourea Organic Catalyst 2 Phenyl isothiocyanate (0.564 g, 4.17 mmol) and p-anisidine (0.510 g, 4.14 mmol) are dissolved in anhydrous dichloromethane and the reaction medium is stirred overnight at room temperature. ambient temperature. The solvent is then evaporated under vacuum and the crude obtained is purified by recrystallization from an EtOH / acetone mixture. The mass of thiourea 2 obtained is 0.48 g. The corresponding molar yield of thiourea 2 is 45% after purification. Crude formula: C 14 H 14 N 2 OS Molecular weight: 258.05 g. mol "1
RMN1 H (δ (ppm), (CD3)2CO, 300 MHz) 8,86 (br.s, 1 H), 7,54-7,52 (m, 1 H), 7,40-7,30 (m, 4H), 7,17- 7,13 (m, 1 H), 6,94-6,89 (m, 2H), 3,80 (s, 3H) 1 H NMR (δ (ppm), (CD 3 ) 2 CO, 300 MHz) 8.86 (br s, 1H), 7.54-7.52 (m, 1H), 7.40-7 , (M, 4H), 7.17-7.13 (m, 1H), 6.94-6.89 (m, 2H), 3.80 (s, 3H)
Exemple 3 : Transformation du fructose mettant en œuyre le catalyseur organique thiourée 1 (conforme) Le catalyseur de l'exemple 1 (0,046 g, 0,12 mmol) est ajouté à une solution de fructose (2,0 g 1 1 ,10 mmol) dans la NMP (20 g). Le rapport massique charge/catalyseur est de 43,5. Le rapport massique solvant/charge est de 10. Le milieu réactionnel est ensuite agité à 120 °C pendant 6 h. La conversion du fructose en 5-HMF est suivi par des prélèvements réguliers d'un aliquot de solution qui est refroidi instantanément à 0°C, redissous dans l'eau et contrôlé par chromatographie ionique. Le rendement en 5-HMF après 6h est de 55%. Exemple 4 : Transformation du fructose mettant en œuyre le catalyseur organique thiourée 2EXAMPLE 3 Transformation of Fructose Using Thiourea Organic Catalyst 1 (Compliant) The catalyst of Example 1 (0.046 g, 0.12 mmol) is added to a solution of fructose (2.0 g, 1.10 mmol). ) in NMP (20 g). The mass ratio filler / catalyst is 43.5. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 120 ° C. for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography. The yield of 5-HMF after 6 hours is 55%. EXAMPLE 4 Transformation of Fructose Using Thiourea Organic Catalyst 2
(conforme) (Compliant)
Le catalyseur de l'exemple 2 (0,044 g, 0,17 mmol) est ajouté à une solution de fructose (2,0 g, 1 1 ,10 mmol) dans la NMP (20 g). Le rapport massique charge/catalyseur est de 45,5. Le rapport massique solvant/charge est de 10. Le milieu réactionnel est ensuite agité à 120 °C pendant 6 h. La conversion du fructose en 5-HMF est suivi par des prélèvements réguliers d'un aliquot de solution qui est refroidi instantanément à 0°C, redissous dans l'eau et contrôlé par chromatographie ionique. Le rendement molaire en 5-HMF après 6h est de 59%. The catalyst of Example 2 (0.044 g, 0.17 mmol) was added to a solution of fructose (2.0 g, 1 1, 10 mmol) in NMP (20 g). The mass ratio filler / catalyst is 45.5. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 120 ° C. for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography. The molar yield of 5-HMF after 6h is 59%.
Exemple 5 : Transformation d'un mélange de glucose et fructose mettant en œuyre le catalyseur organigue thiourée 1 (conforme) EXAMPLE 5 Transformation of a Glucose and Fructose Mixture Using the Thiourea Organic Catalyst 1 (Compliant)
Le catalyseur de l'exemple 1 (0,046 g, 0,12 mmol) est ajouté à un mélange de fructose et de glucose 50% poids/50% poids (2,0 g, 1 1 ,10 mmol) dans la NMP (20 g). Le rapport massique charge/catalyseur est de 43,5. Le rapport massique solvant/charge est de 10. Le milieu réactionnel est ensuite agité à 120 °C pendant 6 h. La conversion du fructose en 5-HMF est suivi par des prélèvements réguliers d'un aliquot de solution qui est refroidi instantanément à 0°C, redissous dans l'eau et contrôlé par chromatographie ionique. Le rendement molaire en 5-HMF après 6h est de 58%. The catalyst of Example 1 (0.046 g, 0.12 mmol) was added to a mixture of fructose and glucose 50% w / wt% (2.0 g, 1 1, 10 mmol) in NMP (20 mmol). boy Wut). The mass ratio filler / catalyst is 43.5. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 120 ° C. for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography. The molar yield of 5-HMF after 6h is 58%.
Exemple 6 : Transformation d'un mélange de glucose et fructose mettant en œuyre le catalyseur organigue thiourée 2 (conforme) EXAMPLE 6 Transformation of a Glucose and Fructose Mixture Using the Thiourea Organic Catalyst 2 (Compliant)
Le catalyseur de l'exemple 2 (0,044 g, 0,17 mmol) est ajouté à un mélange de fructose et de glucose 50% poids/50% poids (2,0 g, 1 1 ,10 mmol) dans la NMP (20 g). Le rapport massique charge/catalyseur est de 45,5. Le rapport massique solvant/charge est de 10. Le milieu réactionnel est ensuite agité à 120 °C pendant 6 h. La conversion du fructose en 5-HMF est suivi par des prélèvements réguliers d'un aliquot de solution qui est refroidi instantanément à 0°C, redissous dans l'eau et contrôlé par chromatographie ionique. Le rendement molaire en 5-HMF après 6h est de 60%. Exemple 7 comparatif : Transformation de fructose sans catalyseur (non conforme) The catalyst of Example 2 (0.044 g, 0.17 mmol) is added to a mixture of fructose and glucose 50% w / wt% (2.0 g, 1 1, 10 mmol) in NMP (20 mg / ml). boy Wut). The mass ratio filler / catalyst is 45.5. The solvent / filler mass ratio is 10. The reaction medium is then stirred at 120 ° C. for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography. The molar yield of 5-HMF after 6 hours is 60%. Comparative Example 7 Transformation of fructose without catalyst (non-compliant)
Le fructose (2,0 g, 1 1 ,10 mmol) est dissous dans la NMP (20 g). Le rapport massique solvant/charge est de 10. Le milieu réactionnel est ensuite agité à 120 °C pendant 6 h. La conversion du fructose en 5-HMF est suivi par des prélèvements réguliers d'un aliquot de solution qui est refroidi instantanément à 0°C, redissous dans l'eau et contrôlé par chromatographie ionique. Le rendement molaire en 5-HMF après 6h est inférieur à 1 %. Exemple 8 comparatif : Transformation de fructose mettant en œuyre une résine acide fort et corrosive (Amberlyst 15), (non conforme) Fructose (2.0 g, 1 1, 10 mmol) is dissolved in NMP (20 g). The solvent / filler mass ratio is 10. The reaction medium is then stirred at 120 ° C. for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography. The molar yield of 5-HMF after 6h is less than 1%. Comparative Example 8: Transformation of Fructose Using a Strong and Corrosive Acid Resin (Amberlyst 15), (Non-Conforming)
L'Amberlyst 15 (0,040 g) est ajoutée à une solution de fructose (2,0 g, 1 1 ,10 mmol) dans la NMP (20 g). Le rapport massique charge/catalyseur est de 50. Le rapport massique solvant/charge est de 10. Le milieu réactionnel est ensuite agité à 120 °C pendant 6 h. La conversion du fructose en 5- HMF est suivi par des prélèvements réguliers d'un aliquot de solution qui est refroidi instantanément à 0°C, redissous dans l'eau et contrôlé par chromatographie ionique. Le rendement molaire en 5-HMF après 6h est de 45%. Amberlyst (0.040 g) is added to a solution of fructose (2.0 g, 1 1, 10 mmol) in NMP (20 g). The mass ratio filler / catalyst is 50. The weight ratio solvent / filler is 10. The reaction medium is then stirred at 120 ° C for 6 h. The conversion of fructose to 5-HMF is followed by regular sampling of an aliquot of solution which is instantly cooled to 0 ° C, redissolved in water and checked by ion chromatography. The molar yield of 5-HMF after 6h is 45%.
Les résultats présentant le rendement en 5-HMF lors du prélèvement réalisé après 6 heures de réaction sont récapitulés dans le Tableau 1 . Les résultats présentant l'évolution du rendement en 5- HMF sur l'ensemble de la durée de réaction sont illustrés en Figure 1 . The results showing the 5-HMF yield during the sample taken after 6 hours of reaction are summarized in Table 1. The results showing the evolution of the yield of 5-HMF over the entire reaction time are illustrated in FIG.
Tableau 1  Table 1
La cinétique de réaction est plus rapide et le rendement en 5-HMF est supérieur dans le cas de l'utilisation de catalyseurs organiques faiblement acides de la famille des thiourées selon l'invention comparativement à un acide sulfonique fort comme l'Amberlyst 15, à savoir environ 60% de rendement molaire en 5-HMF en présence de thiourées contre 45% pour la résine acide forte Amberlyst 15 après 6 heures de réaction. The kinetics of reaction is faster and the yield of 5-HMF is greater in the case of the use of weakly organic organic catalysts of the thiourea family according to the invention compared to a strong sulfonic acid such as Amberlyst 15, namely about 60% molar yield of 5-HMF in the presence of thiourea against 45% for the acidic resin Amberlyst 15 after 6 hours of reaction.
Il paraît donc de manière inattendue par rapport au caractère peu acide, non corrosif et non toxique des thiourées qu'il est nettement avantageux d'utiliser les catalyseurs organiques selon l'invention comparativement à une résine acide forte classiquement utilisée pour la transformation de sucres en 5-HMF. It therefore appears unexpectedly with respect to the low acid, non-corrosive and non-toxic nature of thioureas that it is clearly advantageous to use the organic catalysts according to the invention as compared with a strong acidic resin conventionally used for the conversion of sugars into 5-HMF.

Claims

REVENDICATIONS
1. Procédé de transformation d'une charge comprenant au moins un sucre en 5- hydroxyméthylfurfural, dans lequel ladite charge est mise en contact avec un ou plusieurs catalyseurs organiques en présence d'au moins un solvant, ledit solvant étant l'eau ou un solvant organique seuls ou en mélange, à une température comprise entre 30°C et 200°C, et à une pression comprise entre 0,1 MPa et 10 MPa dans lequel lesdits catalyseurs organiques sont choisis parmi les composés de la famille des thiourées de formule générale R1 NH-C(=S)-NHR2 dans laquelle les groupements R1 et R2 sont choisis parmi les groupements aromatiques comprenant un hétéroatome ou non, les groupements alkyles linéaires ou ramifiés, cycliques ou non cycliques, et les groupements alkyles comportant au moins un hétéroatome, linéaires ou ramifiés, cycliques ou non cycliques, lesdits groupements R1 et R2 pouvant être substitués ou non et identiques ou différents. A process for converting a filler comprising at least one 5-hydroxymethylfurfural sugar, wherein said filler is contacted with one or more organic catalysts in the presence of at least one solvent, said solvent being water or a organic solvent alone or in a mixture, at a temperature of between 30 ° C. and 200 ° C., and at a pressure of between 0.1 MPa and 10 MPa, in which the said organic catalysts are chosen from compounds of the family of thioureas of formula general R 1 NH-C (= S) -NHR 2 in which the groups R 1 and R 2 are chosen from aromatic groups comprising a heteroatom or not, linear or branched alkyl groups, cyclic or non-cyclic, and alkyl groups containing at least one heteroatom, linear or branched, cyclic or non-cyclic, said groups R1 and R2 may be substituted or not and the same or different.
2. Procédé selon la revendication 1 dans lequel ledit sucre est choisi parmi les oligosaccharides et les monosaccharides, seuls ou en mélange. 2. Method according to claim 1 wherein said sugar is selected from oligosaccharides and monosaccharides, alone or in admixture.
3. Procédé selon la revendication 2 dans lequel les monosaccharides sont choisis parmi le glucose, le mannose, le fructose, pris seuls ou en mélange. 3. Process according to claim 2, in which the monosaccharides are chosen from glucose, mannose and fructose, taken alone or as a mixture.
4. Procédé selon la revendication 2 dans lequel les oligosaccharides sont choisis parmi le saccharose, le lactose, le maltose, l'isomaltose, l'inulobiose, le mélibiose, le gentiobiose, le tréhalose, le cellobiose, le cellotriose, le cellotetraose et les oligosaccharides issus de l'hydrolyse desdits polysaccharides issus de l'hydrolyse de l'amidon, de l'inuline, de la cellulose ou de l'hémicellulose, pris seuls ou en mélange. 4. Process according to claim 2, in which the oligosaccharides are chosen from sucrose, lactose, maltose, isomaltose, inulobiosis, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose and oligosaccharides resulting from the hydrolysis of said polysaccharides resulting from the hydrolysis of starch, inulin, cellulose or hemicellulose, taken alone or as a mixture.
5. Procédé selon l'une des revendications 1 à 4 dans lequel lesdits groupements R1 et R2 sont choisis parmi les groupements aromatiques comprenant un hétéroatome, ledit hétéroatome étant choisi parmi l'azote, le phosphore et l'oxygène. 5. Method according to one of claims 1 to 4 wherein said groups R1 and R2 are selected from aromatic groups comprising a heteroatom, said heteroatom being selected from nitrogen, phosphorus and oxygen.
6. Procédé selon la revendication 5, dans lequel lesdits groupements R1 et R2 sont choisis parmi les groupements pyridine, phosphole et furane. 6. Method according to claim 5, wherein said groups R1 and R2 are chosen from pyridine, phosphole and furan groups.
7. Procédé selon les revendications 1 à 4, dans lequel lesdits groupements R1 et R2 sont choisis parmi les groupements aromatiques ne comprenant pas d'hétéroatome ayant de 6 à 14 atomes de carbones, fusionnés ou non. 8. Procédé selon la revendication 7 dans lequel les groupements aromatiques ayant de 6 à 14 atomes de carbones sont choisis parmi les groupements phényle, naphtyle, phénanthryle et anthracyle. 7. Process according to claims 1 to 4, in which the said groups R1 and R2 are chosen from aromatic groups that do not comprise a heteroatom with 6 to 14 carbon atoms, fused or otherwise. 8. Process according to claim 7, in which the aromatic groups having 6 to 14 carbon atoms are chosen from phenyl, naphthyl, phenanthryl and anthracyl groups.
9. Procédé selon les revendications 1 à 4, dans lequel lesdits groupements R1 et R2 sont choisis parmi les groupements alkyles non cycliques ayant de 1 à 12 atomes de carbones linéaires ou ramifiés choisis parmi les groupements méthyle, éthyle, propyle, isopropyle, butyle, pentyle et hexyle. 10. Procédé selon les revendications 1 à 4, dans lequel lesdits groupements R1 et R2 sont choisis parmi les groupements cycloalkyles ayant de 3 à 8 atomes de carbones choisis parmi les groupements cyclopentyle, cyclohexyle, cycloheptyle et bicyclo[2.2.2]octyle. 9. Process according to claims 1 to 4, in which the said groups R1 and R2 are chosen from non-cyclic alkyl groups having from 1 to 12 linear or branched carbon atoms chosen from methyl, ethyl, propyl, isopropyl and butyl groups, pentyl and hexyl. 10. Process according to claims 1 to 4, wherein said groups R1 and R2 are chosen from cycloalkyl groups having from 3 to 8 carbon atoms chosen from cyclopentyl, cyclohexyl, cycloheptyl and bicyclo [2.2.2] octyl groups.
1 1 . Procédé selon les revendications 1 à 4, dans lequel lesdits groupements R1 et R2 sont choisis parmi les groupements alkyles et/ou cycloalkyles comprenant au moins une fonction aminé tertiaire. 1 1. Process according to Claims 1 to 4, in which the said groups R1 and R2 are chosen from alkyl and / or cycloalkyl groups comprising at least one tertiary amine function.
12. Procédé selon la revendication 1 1 , dans lequel lesdits groupements R1 et R2 sont choisis parmi la A/,/V-diméthyléthylamine, la Λ/,/V-diméthylcyclohexylamine, la /V-méthylpipéridine et l'aza- bicyclo[2.2.2]octyle. 12. The process as claimed in claim 11, wherein said R1 and R2 groups are chosen from N, N-dimethylethylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine and azabicyclo [2.2. .2] octyl.
13. Procédé selon les revendications 1 à 4, dans lequel ledit catalyseur organique est la 1 -(3,5-bis- trifluorométhyl-phényl)-3-cyclohexylthiourée. The process according to claims 1 to 4, wherein said organic catalyst is 1- (3,5-bis-trifluoromethyl-phenyl) -3-cyclohexylthiourea.
14. Procédé selon les revendications 1 à 4, dans lequel ledit catalyseur organique est la 1 -(4- méthoxyphényl)-3-phénylthiourée. The process of claims 1 to 4, wherein said organic catalyst is 1- (4-methoxyphenyl) -3-phenylthiourea.
15. Procédé selon l'une des revendications 1 à 7 dans lequel ledit solvant est un solvant organique choisi parmi les alcools, les éthers, les esters, les lactones, les carbonates cycliques, les nitriles, les amides, les sulfones, les sulfoxides et les sels d'ammonium, seuls ou en mélange. 15. Method according to one of claims 1 to 7 wherein said solvent is an organic solvent selected from alcohols, ethers, esters, lactones, cyclic carbonates, nitriles, amides, sulfones, sulfoxides and ammonium salts, alone or as a mixture.
16. Procédé selon la revendication 15 dans lequel les alcools sont choisis parmi le méthanol, l'éthanol, les propanols et les butanols, et dans lequel les éthers sont choisis parmi le diéthyléther, le diméthoxyéthane, le tétrahydrofurane, le dioxane et dans lequel les esters sont choisis parmi le formiate d'éthyle, l'acétate d'éthyle et dans lequel les lactones sont choisis parmi la γ-valérolactone, la γ-butyrolactone et dans lequel les carbonates cycliques sont choisis parmi l'éthylène carbonate, le propylène carbonate et dans lequel les nitriles sont choisis parmi l'acétonitrile, le benzonitrile et dans lequel les amides sont choisies parmi le diméthylformamide, le diéthylformamide, la N-méthylpyrrolidone et dans lequel les sulfones sont choisies parmi la diméthylsulfone, le sulfolane et dans lequel le sulfoxide est le DMSO, et dans lequel le sel d'ammonium est le chlorure de choline, seuls ou en mélange. The process according to claim 15 wherein the alcohols are selected from methanol, ethanol, propanols and butanols, and wherein the ethers are selected from diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane and wherein esters are selected from ethyl formate, ethyl acetate and wherein the lactones are selected from γ-valerolactone, γ-butyrolactone and wherein the cyclic carbonates are selected from ethylene carbonate, propylene carbonate and wherein the nitriles are selected from acetonitrile, benzonitrile and wherein the amides are selected from dimethylformamide, diethylformamide, N-methylpyrrolidone and wherein the sulfones are selected from dimethylsulfone, sulfolane and wherein the sulfoxide is DMSO, and wherein the ammonium salt is choline chloride, alone or in admixture.
17. Procédé selon l'une quelconque des revendications précédentes, dans lequel la température est comprise entre 50°C et 200°C, et dans lequel la pression est comprise entre 0,1 MPa et 8 MPa. 17. A process according to any one of the preceding claims, wherein the temperature is between 50 ° C and 200 ° C, and wherein the pressure is between 0.1 MPa and 8 MPa.
8. Procédé selon l'une quelconque des revendications précédentes, dans lequel la charge est introduite à un rapport massique solvant/charge compris entre 0,1 et 200. 8. Process according to any one of the preceding claims, in which the filler is introduced at a solvent / charge mass ratio of between 0.1 and 200.
9. Procédé selon l'une quelconque des revendications précédentes, dans lequel les catalyseurs organiques de la famille des thiourées sont introduits à un rapport massique charge/catalyseur(s) organique(s) compris entre 1 et 1000. 9. Process according to any one of the preceding claims, in which the organic catalysts of the family of thioureas are introduced at a mass ratio filler / organic catalyst (s) of between 1 and 1000.
EP16741608.0A 2015-07-24 2016-07-19 Method for producing 5-(hydroxymethyl)furfural in the presence of organic catalysts of the thiourea family Withdrawn EP3325458A1 (en)

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