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WO2014078982A1 - Procédé d'obtention de 5-hydroxyméthylfurfural - Google Patents

Procédé d'obtention de 5-hydroxyméthylfurfural Download PDF

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Publication number
WO2014078982A1
WO2014078982A1 PCT/CN2012/084870 CN2012084870W WO2014078982A1 WO 2014078982 A1 WO2014078982 A1 WO 2014078982A1 CN 2012084870 W CN2012084870 W CN 2012084870W WO 2014078982 A1 WO2014078982 A1 WO 2014078982A1
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WO
WIPO (PCT)
Prior art keywords
ntf
process according
formula
catalyst
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2012/084870
Other languages
English (en)
Inventor
Damien Cartigny
Jean Marc Clacens
Floryan Decampo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Rhodia Operations SAS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Rhodia Operations SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Rhodia Operations SAS filed Critical Centre National de la Recherche Scientifique CNRS
Priority to PCT/CN2012/084870 priority Critical patent/WO2014078982A1/fr
Publication of WO2014078982A1 publication Critical patent/WO2014078982A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention concerns a process for the production of 5- hydroxymethylfurfural (HMF) from a hexose via a catalytic dehydration reaction in the presence of bis(perfraoroalkylsulfonimide) acid or salts thereof catalysts, and derivatives.
  • HMF 5- hydroxymethylfurfural
  • HMF 5-Hydroxymethylfurfural
  • FDCA 2,5-furandicarboxylic acid
  • Solid acid catalysts for example, ion exchange resin, H-zeolite, metal sulfated, zirconium phosphate, niobic acid, and niobium phosphate overcome some restrictions of mineral acids mentioned above. Nevertheless, solid acid catalysts also possess some drawbacks because of relatively lower fructose conversions and longer reaction times.
  • the present invention concerns then a process for the production of 5- hydroxymethylfurfural (HMF) from a compound of formula (I) or its corresponding cyclic five-membered structure, via a catalytic dehydration reaction in the presence of catalyst of formula (II) Formula (I):
  • R 1 is H or OH
  • R 2 is H or OH
  • RF and R'F which are identical or different, each represent a perhalogen radical
  • M is H or a metal element chosen from alkali metal, alkali earth metal, transition metal and lanthanide metal
  • n is an integer equal to the valence of M.
  • the present invention also concerns a HMF susceptible to be obtained according to the process of the invention.
  • Dehydration reaction of the present invention is defined as a chemical reaction that involves the loss of water from the reacting molecule. Dehydration reactions are a subset of elimination reactions involving one or several hydroxyl group(s) (-OH). Formula (I)
  • D-glucose is the cyclic six-membered structure of the D-fructose.
  • D-fructopyranose exists as a mixture generally comprising 70% D- fructopyranose and about 22% D-fructofuranose.
  • the open isomer D-glucose gives rise to two distinct cyclic forms: D-glucopyranose, and D- glucofuranose.
  • Concentration of compound of formula (I) may be comprised between 0.001 and 10 mol.L "1 , when a solvent is used in the reaction medium.
  • RF and R'F which are identical or different, represent a perhalogen radical, which is preferably having from 1 to 12 carbon atoms.
  • Halogen atoms in the perhalogen radicals may be for example F or CI.
  • RF and R'F which are identical or different, represent CF 3 .
  • Metal elements of the periodic table may be chosen in the group consisting of:
  • alkali metals such as K or Cs
  • alkaline earth metals such as Ca
  • lanthanides such as La or Ce
  • transition metals such as Ti, Y, n, Cu or Fe.
  • Metal elements M of period 4 are particularly preferred, such as Ca and Cu.
  • Catalysts of the present invention are preferably chosen in the group consisting of: H(NTf 2 ), (NTf 2 ) 5 Y(NTf 2 ) 3 , La(NTf 2 ) 3 , Zn(NTf 2 ) 2 , Cs(NTf 2 ), Ca(NTf 2 ) 2 , Fe(NTf 2 ) 3 , Cu(NTf 2 ) 2 , Ti(NTf 2 ) 4 and Ce(NTf 2 ) 3 .
  • a combination of two or more catalysts of the present invention may be used during the reaction of the present invention, notably in blend.
  • a combination of H(NTf 2 ) and Cu(NTf 2 ) 2 is particularly preferred.
  • Catalyst loading during the reaction may be comprised between 0.01 and 100 mol%, preferably between 1 and 30, in relation with the molar amount of the compound of formula (I).
  • Catalyst of the invention may be used in a homogeneous or heterogeneous way.
  • Catalyst may be supported on a carrier, such as for example one of the oxides, carbons or organic or inorganic resins.
  • the carrier may be selected from the group consisting of silica, alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, yttria, zeolite, perovskite, silica clay, and iron oxide and mixtures thereof.
  • the catalyst may be supported on a carrier in any convenient fashion, particularly by adsorption, ion-exchange, grafting, trapping, impregnation, or sublimation ⁇
  • Reaction of the present invention may be carried out by using a catalyst- ligand complex in which catalyst is the compound of formula (II).
  • ligand is preferably chosen in the family of carbene ligand, ⁇ - type ligand phosphorous ligand, oxygen ligand and nitrogen ligand.
  • Suitable ligands to be used according to the present mvention are phosphorus ligands such as halophosphites such as fluorophosphites, phosphites, phosphinites, phosphonites, and phosphine.
  • Monodentate phosphine ligands and bidentate diphosphine ligand such as xantphos are particularly preferred.
  • the catalyst-ligand complex may be prepared before the start of the reaction of the present invention or in situ at the start or during the reaction.
  • the process of the present invention may be carried out without solvent. It is also possible to use a solvent or a combination of solvents for the reaction, preferably solvents able to dissolve the compound of formula (I) and also solvent able to dissolve the compound of formula (I) and the compound of formula (II).
  • a solvent or a combination of solvents for the reaction preferably solvents able to dissolve the compound of formula (I) and also solvent able to dissolve the compound of formula (I) and the compound of formula (II).
  • Preferred solvents used in the reaction medium of the present invention are polar aprotic solvent, more preferably selected among:
  • linear ethers such as diethylether, dimethoxyethane or cyclic ethers, such as tetrahydrofuran, dioxane or dimethyltetrahydrofuran,
  • esters such as methyl or ethyl formate, propylene or ethylene carbonate, or butyrolactones,
  • nitrate derivatives such as nitromethane or nitrobenzene
  • amides such as dimethylformamide, diethylformamide and N- methylpyrolidone
  • sulfones such as dimethyl sulfone, tetramethylene sulfone and other sulfolanes.
  • the medium of the reaction comprises a polar aprotic solvent
  • said medium comprises less than 10 wt % of water, notably at the start of the reaction.
  • the temperature at which reaction is performed may vary in a large range, but in general it is preferred that the reaction is carried out at a temperature from 0 and 300°C, more preferably between 50 and 150°C. Temperatures may be reached either thermically or by microwave irradiation. Pressure range of the reaction may be comprised between 1 and 100 bar. Reaction of the present invention may be carried out for a range time comprised between 10 min to 24 hours.
  • This reaction may be conducted in any conventional equipment suitable to effect production of HMF. This reaction may be carried out in a continuous or a discontinuous fashion.
  • suitable equipments include a stirred tank or loop reactor.
  • End of reaction may be carried out by stop of the temperature and cooling of the reaction medium, notably air cooling.
  • the efficiency of the process of the present invention can be monitored by any conventional analytical means, such as Infrared spectroscopy, NMR, Raman spectroscopy, GC and HPLC.
  • catalysts may be eventually neutralized and/or removed by distillation, extraction or washings. Said catalysts may notably be recycled to the reactor.
  • HMF of interest can be purified by well known methods of the technical field, such as distillation, crystallization, liquid extraction or extraction with a polymer to adsorb HMF.
  • distillation, crystallization, liquid extraction or extraction with a polymer to adsorb HMF can be purified by well known methods of the technical field, such as distillation, crystallization, liquid extraction or extraction with a polymer to adsorb HMF.
  • the examples provided here further describe and demonstrate embodiments of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitation of the present invention
  • diphosphine ligand such as Xantphos is efficiently activating Ti(NTf 2 ) 4 and Cu(NTf 2 ) 2 that permits to provide a higher yield to the reaction while avoiding generation of formic acid.

Landscapes

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

Abstract

La présente invention concerne un procédé d'obtention de 5-hydroxyméthylfurfural (HMF) à partir d'un hexose par l'intermédiaire d'une réaction de déshydratation catalytique en présence d'acide bis(perfluoroalkyle sulfonamide) ou de ses sels et de catalyseurs, ainsi que ses dérivés.
PCT/CN2012/084870 2012-11-20 2012-11-20 Procédé d'obtention de 5-hydroxyméthylfurfural Ceased WO2014078982A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2012/084870 WO2014078982A1 (fr) 2012-11-20 2012-11-20 Procédé d'obtention de 5-hydroxyméthylfurfural

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2012/084870 WO2014078982A1 (fr) 2012-11-20 2012-11-20 Procédé d'obtention de 5-hydroxyméthylfurfural

Publications (1)

Publication Number Publication Date
WO2014078982A1 true WO2014078982A1 (fr) 2014-05-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2012/084870 Ceased WO2014078982A1 (fr) 2012-11-20 2012-11-20 Procédé d'obtention de 5-hydroxyméthylfurfural

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WO (1) WO2014078982A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160028078A (ko) 2014-09-02 2016-03-11 한국화학연구원 5-히드록시메틸푸푸랄의 제조방법
FR3039152A1 (fr) * 2015-07-24 2017-01-27 Ifp Energies Now Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des sulfonamides

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102399203A (zh) * 2011-12-19 2012-04-04 浙江大学 一种离子液体降解碳水化合物制备5-羟甲基糠醛的方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102399203A (zh) * 2011-12-19 2012-04-04 浙江大学 一种离子液体降解碳水化合物制备5-羟甲基糠醛的方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
WANG, FENFEN ET AL.: "Dehydration of fructose to 5-hydroxymethylfurfural by rare earth metal trifluoromethanesulfonates in organic solvents", CARBOHYDRATE RESEARCH, vol. 346, 10 March 2011 (2011-03-10), pages 982 - 985, XP028191370, DOI: doi:10.1016/j.carres.2011.03.009 *
ZHANG, YANMEI E ET AL.: "Molecular aspects of glucose dehydration by chromium chlorides in ionic liquids", CHEM. EUR. J., vol. 17, 2011, pages 5281 - 5288 *
ZHANG, ZEHUI ET AL.: "Catalytic conversion of carbohydrates into 5-hydroxymethylfurfural by germanium(IV) chloride in ionic liquids", CHEMSUSCHEM, vol. 4, 2011, pages 131 - 138 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160028078A (ko) 2014-09-02 2016-03-11 한국화학연구원 5-히드록시메틸푸푸랄의 제조방법
FR3039152A1 (fr) * 2015-07-24 2017-01-27 Ifp Energies Now Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des sulfonamides
WO2017016925A1 (fr) * 2015-07-24 2017-02-02 IFP Energies Nouvelles Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des sulfonamides

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