FR3008409A1 - PROCESS FOR THE PRODUCTION OF 2,5-DICARBOXALDEHYDE FURANE FROM HYDROXYMETHYLFURFURAL AND HALOGENATED DERIVATIVES NOT USING METAL CATALYST - Google Patents
PROCESS FOR THE PRODUCTION OF 2,5-DICARBOXALDEHYDE FURANE FROM HYDROXYMETHYLFURFURAL AND HALOGENATED DERIVATIVES NOT USING METAL CATALYST Download PDFInfo
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- FR3008409A1 FR3008409A1 FR1301696A FR1301696A FR3008409A1 FR 3008409 A1 FR3008409 A1 FR 3008409A1 FR 1301696 A FR1301696 A FR 1301696A FR 1301696 A FR1301696 A FR 1301696A FR 3008409 A1 FR3008409 A1 FR 3008409A1
- Authority
- FR
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- Prior art keywords
- hmf
- hydroxymethylfurfural
- dmso
- mol
- fdc
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims description 39
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims description 35
- 239000003054 catalyst Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title description 9
- 239000002184 metal Substances 0.000 title description 7
- 229910052751 metal Inorganic materials 0.000 title description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title description 5
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 62
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- -1 halide salts Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 abstract description 3
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 12
- 229930091371 Fructose Natural products 0.000 description 11
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 11
- 239000005715 Fructose Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 2
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HJYHSCTYDCMXPG-UHFFFAOYSA-N 5-(bromomethyl)furan-2-carbaldehyde Chemical compound BrCC1=CC=C(C=O)O1 HJYHSCTYDCMXPG-UHFFFAOYSA-N 0.000 description 1
- KAZRCBVXUOCTIO-UHFFFAOYSA-N 5-(chloromethyl)furan-2-carbaldehyde Chemical compound ClCC1=CC=C(C=O)O1 KAZRCBVXUOCTIO-UHFFFAOYSA-N 0.000 description 1
- BOQNBJCFILUPHH-UHFFFAOYSA-N 5-(iodomethyl)furan-2-carbaldehyde Chemical compound ICC1=CC=C(C=O)O1 BOQNBJCFILUPHH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
Abstract
Procédé de préparation de furane 2,5-dicarboxaldéhyde qui consiste à mettre en réaction le HMF ou un dérivé halogéné du HMF dans un solvant de la famille des sulfoxydes à une température comprise entre 50 et 200°C pendant une durée comprise entre 1 et 36 heures.A process for the preparation of furan 2,5-dicarboxaldehyde which comprises reacting HMF or a halogenated derivative of HMF in a solvent of the family of sulfoxides at a temperature between 50 and 200 ° C for a period of time between 1 and 36 hours.
Description
Procédé de fabrication de furane 2,5-dicarboxaldéhyde à partir d'hydroxyméthylfurfural et de ses dérivés halogénés n'utilisant pas de catalyseur métallique L'hydroxyméthylfurfural (HMF) peut être synthétisé à partir de substances d'origine végétale contenant ou pouvant libérer des sucres tels que le glucose ou le fructose, par exemple l'inuline ou la cellulose., Le HMF constitue un produit de départ dans la synthèse de nombreux dérivés furaniques qui, à leur tour peuvent servir dans la production de polymères qui présentent des propriétés intéressantes. Parmi les nombreux dérivés du HMF, le furane 2,5-dicarboxaldéhyde (FDC) est un monomère qui peut faire l'objet de nombreuses applications. En particulier, il peut servir : pour la synthèse de certains polymères et de macrocycles, notamment dans le domaine pharmaceutique d'agent de réticulation dans la préparation de polymères spéciaux ; de liant dans les sables de fonderie ; pour la fabrication de la pellicule de séparation des solutions aqueuses des batteries alcalines ; d'agent d'inhibition de corrosion ; d'agent de traitement de surface de métaux tels que le cuivre, le nickel ; d'intermédiaire de synthèse d'autres composés furaniques symétriques ou dissymétriques tels que l'acide furane 2,5-dicarboxylique (FDA), le furane 2,5-diméthylamine. La fabrication du FDC est largement documentée mais n'est actuellement pas réalisée industriellement par absence de procédé économiquement viable. Les procédés connus de synthèse du FDC sont soit des réactions stoechiométriques, soit des réactions en catalyse homogène utilisant des métaux souvent toxiques. Les réactions d'oxydation du HMF en catalyse hétérogène posent a priori des difficultés dans la , mesure où le HMF n'est pas stable aux hautes températures (sa dégradation intervenant à partir de 100 °C) nécessaires à l'activation des catalyseurs solides d'oxydation.Process for manufacturing furan 2,5-dicarboxaldehyde from hydroxymethylfurfural and its halogenated derivatives not using a metal catalyst Hydroxymethylfurfural (HMF) can be synthesized from substances of vegetable origin containing or capable of releasing sugars such as glucose or fructose, for example inulin or cellulose. HMF is a starting material in the synthesis of many furan derivatives which, in turn, can be used in the production of polymers which have interesting properties. Among the many derivatives of HMF, furan 2,5-dicarboxaldehyde (FDC) is a monomer that can be the subject of many applications. In particular, it can be used: for the synthesis of certain polymers and macrocycles, especially in the pharmaceutical field of crosslinking agent in the preparation of special polymers; binder in foundry sands; for the manufacture of the separation film of aqueous solutions of alkaline batteries; corrosion inhibiting agent; metal surface treating agent such as copper, nickel; synthesis intermediate of other symmetrical or asymmetric furanic compounds such as furan 2,5-dicarboxylic acid (FDA), furan 2,5-dimethylamine. The manufacture of FDC is widely documented but is not currently carried out industrially by lack of economically viable process. The known processes for synthesizing FDC are either stoichiometric reactions or reactions in homogeneous catalysis using metals which are often toxic. The oxidation reactions of HMF in heterogeneous catalysis pose a priori difficulties in that HMF is not stable at high temperatures (its degradation occurring from 100 ° C) necessary for the activation of solid catalysts. 'oxidation.
Il semble donc intéressant de réaliser la synthèse de FDC par oxydation du HMF sans avoir recours à un catalyseur métallique. Un tel procédé est décrit dans le brevet français FR2669636. Ce procédé réalise la transformation du HMF dans un mélange de solvants en présence d'un agent électrophile tel que l'anhydride acétique. Le mélange de solvants est composé d'un solvant de la famille des sulfoxydes tel que le diméthylsulfoxyde (DMSO) et d'un solvant tiers appartenant au groupe suivant : diéthylcétone, méthylisobutylcétone, dichlorométhane ou acétate d'éthyle. L'emploi du tiers solvant complique la mise en oeuvre du procédé notamment lors de la récupération du FDC. L'agent électrophile est utilisé à une quantité comprise entre 1 et 5 équivalents molaires par rapport au HMF et sa récupération n'a pas été prouvée ce qui rend le procédé non rentable sur le plan économique. La présente invention concerne donc un procédé perfectionné de fabrication de FDC à partir de HMF et n'ayant recours ni à un catalyseur métallique ni à un tiers solvant. Ce procédé n'emploie pas non plus d'agent électrophile en quantité stoechiométrique par rapport au HMF. L'invention permet ainsi de lever les différents défauts du procédé décrit dans le brevet FR2669636. Le procédé de l'invention est caractérisé en ce qu'il 25 consiste à oxyder le HMF ou au moins un de ses dérivés halogénés en FDC dans un solvant de la famille des sulfoxydes. Cette oxydation est réalisée à une température comprise entre 50 et 200 °C pendant une durée comprise entre 1 et 36 heures. 30 On entend par dérivé halogéné du HMF, un composé choisi parmi : le 5-chloro-methy1-2-furfural (Cl-HMF), le 5-bromomethy1-2-furfural (Br-HMF), le 5-iodo-methy1-2-furfural (IHMF), le 5-fluoro-methy1-2-furfural (F-HMF).It therefore seems interesting to carry out the synthesis of FDC by oxidation of HMF without resorting to a metal catalyst. Such a process is described in French patent FR2669636. This process converts HMF into a solvent mixture in the presence of an electrophilic agent such as acetic anhydride. The solvent mixture is composed of a solvent of the family of sulfoxides such as dimethylsulfoxide (DMSO) and a third solvent belonging to the following group: diethyl ketone, methyl isobutyl ketone, dichloromethane or ethyl acetate. The use of the solvent third complicates the implementation of the method especially during the recovery of the FDC. The electrophilic agent is used in an amount of between 1 and 5 molar equivalents relative to the HMF and its recovery has not been proven which renders the process economically unprofitable. The present invention therefore relates to an improved method of manufacturing FDC from HMF and using neither a metal catalyst nor a third solvent. This method also does not use an electrophilic agent in stoichiometric amount relative to the HMF. The invention thus makes it possible to remove the various defects of the process described in the patent FR2669636. The process of the invention is characterized in that it comprises the oxidation of HMF or at least one of its halogenated derivatives to FDC in a solvent of the family of sulfoxides. This oxidation is carried out at a temperature of between 50 and 200 ° C. for a duration of between 1 and 36 hours. Halogenated derivative of HMF is a compound selected from: 5-chloro-methyl-2-furfural (Cl-HMF), 5-bromomethyl-2-furfural (Br-HMF), 5-iodo-methy1 -2-furfural (IHMF), 5-fluoro-methyl-2-furfural (F-HMF).
Ce procédé permet d'obtenir des rendements en FDC allant jusqu'à 100 % sans avoir recours à un catalyseur métallique ou et un agent électrophile. Selon un mode de mise oeuvre préféré du procédé, 5 l'oxydation est réalisée dans le DMSO comme solvant. De préférence, le HMF ou au moins un de ses dérivés halogénés sera alors préalablement solubilisé dans le DMSO à une concentration comprise entre 0,009 et 2,62 mol/l. Il est également possible de préparer le HMF par une des nombreuses 10 méthodes de l'état de l'art permettant de déshydrater des sucres dans le DMSO, notamment celles décrites dans le brevet FR2669636. Selon un mode de mise oeuvre préféré du procédé, 15 l'oxydation est réalisée en présence de 1 à 50 % molaire par rapport au HMF ou à son dérivé halogéné, d'au moins un catalyseur choisi parmi les acides minéraux ou les sels d'halogénure. Selon un mode de mise oeuvre préféré du procédé, on 20 utilise entre 10 et 30 % molaire par rapport au HMF ou son dérivé halogéné d'au moins un catalyseur choisi parmi l'acide sulfurique, l'acide bromhydrique, ou le bromure de sodium. Selon un mode de mise oeuvre préféré du procédé, on 25 réalise la transformation du HMF ou dérivé halogéné à une température comprise entre 125 et 175 °C pendant une durée comprise entre 6 et 24 heures. Le FDC obtenu en fin de procédé pourra être récupéré après distillation sous pression réduite du DMSO 30 éventuellement après filtration ou neutralisation du catalyseur. On pourra également utiliser le FDC récupéré ou en solution dans le DMSO pour réaliser son oxydation en acide furane 2,5 dicarboxylique (FDCA). Afin d'illustrer le procédé correspondant à la présente 35 invention, les exemples suivants sont rapportés.This process provides FDC yields of up to 100% without the use of a metal catalyst or an electrophilic agent. According to a preferred embodiment of the process, the oxidation is carried out in DMSO as a solvent. Preferably, the HMF or at least one of its halogenated derivatives will then be solubilized beforehand in DMSO at a concentration of between 0.009 and 2.62 mol / l. It is also possible to prepare HMF by one of the many state-of-the-art methods for dehydrating sugars in DMSO, including those described in FR2669636. According to a preferred mode of implementation of the process, the oxidation is carried out in the presence of 1 to 50 mol% relative to the HMF or its halogenated derivative, of at least one catalyst chosen from mineral acids or salts thereof. halide. According to a preferred embodiment of the process, between 10 and 30 mol% relative to the HMF or its halogenated derivative of at least one catalyst chosen from sulfuric acid, hydrobromic acid or sodium bromide is used. . According to a preferred embodiment of the process, the HMF or halogenated derivative is converted at a temperature of between 125 and 175 ° C. for a period of between 6 and 24 hours. The FDC obtained at the end of the process can be recovered after distillation under reduced pressure of the DMSO 30 optionally after filtration or neutralization of the catalyst. It will also be possible to use the FDC recovered or in solution in DMSO to carry out its oxidation to 2,5-dicarboxylic furan acid (FDCA). In order to illustrate the process of the present invention, the following examples are reported.
Exemple 1 : Procédé de préparation du FDC à partir du HMF sans catalyseur On prépare une solution de HMF dans le DMSO (0,5 mol/1 de HMF). Apres dissolution totale du HMF, le milieu réactionnel est mis sous agitation à une température de 150 00 pendant 18 h.Example 1 Method for Preparing FDC from HMF Without Catalyst A solution of HMF in DMSO (0.5 mol / l of HMF) is prepared. After total dissolution of the HMF, the reaction medium is stirred at a temperature of 150 ° C. for 18 h.
Le rendement en FDC, mesuré par CPG est de 40 %. Exemple 2 : Procédé de préparation du FDC à partir du RMF On prépare une solution de HMF dans un solvant organique (0,50 mol/1 de HMF dans le DMSO, 0,50 mol/1 de HMF dans le DMF, 0,20 mol/1 de HMF dans le diphénylsulfoxyde, 0,30 mol/1 de HMF dans le méthylphénylsulfoxyde, 0,37 mol/1 de HMF dans le sulfolane). Apres dissolution totale du HMF, le catalyseur (30 % molaire par rapport au HMF) est ajouté au mélange. Le milieu réactionnel est mis sous agitation à une température de 150 °C pendant 18 h. Le rendement en FDC est mesuré par CPG ou par RMN après 25 addition d'eau et extraction à l'acétate d'éthyle. Les résultats sont regroupés au tableau suivant : 30 35 Entrée Catalyseur Solvant Rendement FDC (%) 1 H2SO4 DMSO 64 2 APTS DMSO 39 3 HC1 DMSO 38 4 HI DMSO 63 5 HBr DMSO 100 6 NaI DMSO 7 7 NaC1 DMSO 10 8 NH4Br DMSO 71 9 LiBr DMSO 76 10 NaBr DMSO 100 11 NaBr/H2504 DMSO 100 12 NaBr DMF 10 13 NaBr diphényl 24 sulfoxyde 14 NaBr Me-phényl 29 sulfoxyde 15 NaBr Sulfolane 16 APTS: acide para-toluène sulfonique DMF: Diméthylformamide Me-phényl sulfoxyde: méthyl phényl sulfoxyde Exemple 3 : Procédé de préparation du FDC à partir d'un dérivé halogéné du }IMF On prépare une solution de dérivé du HMF dans du DMSO (0,5 mol/1 de Br-HMF dans le DMSO, 0,5 mol/1 de Cl-HMF dans le DMSO, 0,5 mol/1 de I-HMF dans le DMSO). Apres dissolution totale le milieu réactionnel est mis sous agitation à une température de 150 °C pendant 18 h. Le rendement en FDC est mesuré par CPG ou par RMN après 35 addition d'eau et extraction à l'acétate d'éthyle.The FDC yield measured by GC is 40%. Example 2 Method for Preparing FDC from RMF A solution of HMF in an organic solvent (0.50 mol / l of HMF in DMSO, 0.50 mol / l of HMF in DMF, 0.20 mol / l of HMF in diphenylsulfoxide, 0.30 mol / l of HMF in methylphenylsulfoxide, 0.37 mol / l of HMF in sulfolane). After total dissolution of the HMF, the catalyst (30 mol% relative to the HMF) is added to the mixture. The reaction medium is stirred at a temperature of 150 ° C. for 18 h. FDC yield is measured by GPC or NMR after water addition and ethyl acetate extraction. The results are summarized in the following table: Catalyst entry Solvent Yield FDC (%) 1 H2SO4 DMSO 64 2 APTS DMSO 39 3 HC1 DMSO 38 4 HI DMSO 63 5 HBr DMSO 100 6 NaI DMSO 7 7 NaCl DMSO 10 8 NH4Br DMSO 71 LiBr DMSO 76 NaBr DMSO 100 11 NaBr / H2504 DMSO 100 12 NaBr DMF 10 13 NaBr Diphenyl Sulfoxide 14 NaBr Me-phenyl Sulfoxide NaBr Sulfolane 16 APTS: para-toluene sulfonic acid DMF: Dimethylformamide Me-phenyl sulfoxide: methyl phenyl sulfoxide Example 3: Process for preparing FDC from a halogenated derivative of MFI A solution of HMF derivative in DMSO (0.5 mol / l of Br-HMF in DMSO, 0.5 mol / 1 Cl-HMF in DMSO, 0.5 mol / l I-HMF in DMSO). After complete dissolution, the reaction mixture is stirred at a temperature of 150 ° C. for 18 h. The FDC yield is measured by GPC or NMR after water addition and ethyl acetate extraction.
Entrée Dérivé Rendement FDC (%) 1 Br-HMF 57 2 Cl-HMF 81 3 I-HMF 62 Br-HMF : 5-bromométhylfurfural Cl-HMF : 5-chlorométhylfurfural I-HMF : 5-iodométhylfurfural Exemple 4 : Procédé de préparation du FDC one pot à partir du Fructose. On prépare une solution de fructose dans le DMSO (0,5 mol/1 de fructose). Apres dissolution totale du fructose, le mélange est chauffé à 150 °C. La température est maintenue pendant 5 h. Le mélange est refroidie à TA. Lorsqu'il est présent, le catalyseur est ajouté (30 % molaire par rapport au Fructose). Le milieu réactionnel est mis sous agitation à 150°C pendant 18 heures. Le rendement en FDC est mesuré par CPG ou par RMN après addition d'eau et extraction à l'acétate d'éthyle.Derived Entry Yield FDC (%) 1 Br-HMF 57 2 Cl-HMF 81 3 I-HMF 62 Br-HMF: 5-bromomethylfurfural Cl-HMF: 5-chloromethylfurfural I-HMF: 5-iodomethylfurfural Example 4: Preparation process FDC one pot from Fructose. A solution of fructose in DMSO (0.5 mol / l fructose) is prepared. After complete dissolution of the fructose, the mixture is heated to 150 ° C. The temperature is maintained for 5 hours. The mixture is cooled to RT. When present, the catalyst is added (30 mol% relative to Fructose). The reaction medium is stirred at 150 ° C. for 18 hours. The yield of FDC is measured by GPC or NMR after addition of water and extraction with ethyl acetate.
Entrée Catalyseur Rendement FDC (%) 1 12 2 KBr 57 3 FeBr2 68 4 CuBr2 54 5 NaBr 60 6 HBr 68 Exemple 5 : Procédé de préparation du FDC one pot à partir du Fructose On prépare une solution de fructose dans le DMSO (0,5 mol/1 5 de fructose). Apres dissolution totale du fructose, le catalyseur (30 % molaire de NaBr par rapport au fructose) est ajouté et le mélange est chauffé à 150 °C pendant 24 h. Le rendement en FDC (68%) est mesuré par CPG.Catalyst input Yield FDC (%) 1 12 2 KBr 57 3 FeBr2 68 4 CuBr2 54 5 NaBr 60 6 HBr 68 Example 5: Process for preparing the one-pot FDC from Fructose A solution of fructose in DMSO (0, 5 mol / 1 of fructose). After complete dissolution of the fructose, the catalyst (30 mol% of NaBr relative to fructose) is added and the mixture is heated at 150 ° C. for 24 hours. The FDC yield (68%) is measured by GIC.
10 Exemple 6 : Procédé de préparation du FDA à partir du FDC On prépare une solution aqueuse ou organique (DMSO) 15 contenant du FDC (0,40 mol/1 de FDC dans l'eau, 0,20 mol/1 de FDC dans le DMSO). On ajoute 2,5 équivalents molaires d'acétate de sodium puis 7,5 équivalents molaires de peroxyde d'hydrogène. La solution est maintenue à 60 °C pendant 18 h.Example 6: Process for preparing FDA from FDC An aqueous or organic solution (DMSO) containing FDC (0.40 mol / l of FDC in water, 0.20 mol / l of FDC in DMSO). 2.5 molar equivalents of sodium acetate and 7.5 molar equivalents of hydrogen peroxide are added. The solution is kept at 60 ° C for 18 h.
20 Le rendement en FDA est déterminé après addition d'eau acide et extraction par l'acétate d'éthyle. Entrée solvant Rendement FDA (%) 25 1 eau 75 2 DMSO 68 30 35The yield of FDA is determined after addition of acidic water and extraction with ethyl acetate. Solvent inlet Yield FDA (%) 25 1 water 75 2 DMSO 68 30 35
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| WO2019149853A1 (en) | 2018-01-31 | 2019-08-08 | Avantium Knowledge Centre B.V. | A process for the conversion of a solid lignocellulosic material |
| WO2019149843A1 (en) | 2018-01-31 | 2019-08-08 | Avantium Knowledge Centre B.V. | Process for the conversion of a solid lignocellulosic material |
| US11332454B2 (en) | 2018-01-31 | 2022-05-17 | Furanix Technologies B.V. | Process for the conversion of a solid lignocellulosic material |
| US11578046B2 (en) | 2018-01-31 | 2023-02-14 | Furanix Technologies B.V. | Process for the conversion of a solid lignocellulosic material |
| WO2021251633A1 (en) * | 2020-06-12 | 2021-12-16 | 코오롱인더스트리 주식회사 | Method and system for manufacturing dicarboxylic acid aromatic heterocyclic compound |
| WO2023008611A1 (en) * | 2021-07-28 | 2023-02-02 | 코오롱인더스트리 주식회사 | Dicarboxyl acid aromatic heterocyclic compound and method for preparing same |
| WO2023008610A1 (en) * | 2021-07-28 | 2023-02-02 | 코오롱인더스트리 주식회사 | Catalyst for making dicarboxyl acid aromatic heterocyclic compound, and method for preparing dicarboxyl acid aromatic heterocyclic compound |
| CN116606267A (en) * | 2023-05-23 | 2023-08-18 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan dicarboxaldehyde from 5-hydroxymethyl furfural |
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