WO2017016924A1 - Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees - Google Patents
Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees Download PDFInfo
- Publication number
- WO2017016924A1 WO2017016924A1 PCT/EP2016/067126 EP2016067126W WO2017016924A1 WO 2017016924 A1 WO2017016924 A1 WO 2017016924A1 EP 2016067126 W EP2016067126 W EP 2016067126W WO 2017016924 A1 WO2017016924 A1 WO 2017016924A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- groups
- chosen
- process according
- cyclic
- solvent
- Prior art date
Links
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
- 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.
- 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 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.
- 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.
- 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 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.
Landscapes
- 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)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Furan Compounds (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018502816A JP2018526342A (ja) | 2015-07-24 | 2016-07-19 | チオウレア群からの有機触媒の存在下での5−ヒドロキシメチルフルフラールの製造方法 |
BR112018000195A BR112018000195A2 (pt) | 2015-07-24 | 2016-07-19 | processo de produção de 5-hidroximetilfurfural em presença de catalisadores orgânicos da família das tioureias |
US15/747,343 US10239852B2 (en) | 2015-07-24 | 2016-07-19 | Process for the production of 5-hydroxymethylfurfural in the presence of organic catalysts from the thiourea family |
CN201680043452.5A CN108137524A (zh) | 2015-07-24 | 2016-07-19 | 在来自硫脲类的有机催化剂的存在下生产5-羟甲基糠醛的方法 |
EP16741608.0A EP3325458A1 (fr) | 2015-07-24 | 2016-07-19 | Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees |
KR1020187002190A KR20180034422A (ko) | 2015-07-24 | 2016-07-19 | 티오우레아 패밀리의 유기 촉매의 존재 하에서의 5-(하이드록시메틸)푸르푸랄의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1557052 | 2015-07-24 | ||
FR1557052A FR3039150B1 (fr) | 2015-07-24 | 2015-07-24 | Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017016924A1 true WO2017016924A1 (fr) | 2017-02-02 |
Family
ID=54545260
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2016/067126 WO2017016924A1 (fr) | 2015-07-24 | 2016-07-19 | Procede de production de 5-hydroxymethylfurfural en presence de catalyseurs organiques de la famille des thiourees |
Country Status (8)
Country | Link |
---|---|
US (1) | US10239852B2 (fr) |
EP (1) | EP3325458A1 (fr) |
JP (1) | JP2018526342A (fr) |
KR (1) | KR20180034422A (fr) |
CN (1) | CN108137524A (fr) |
BR (1) | BR112018000195A2 (fr) |
FR (1) | FR3039150B1 (fr) |
WO (1) | WO2017016924A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3076554A1 (fr) * | 2018-01-10 | 2019-07-12 | IFP Energies Nouvelles | Procede de production de 5-hydroxymethylfurfural |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006063220A2 (fr) * | 2004-12-10 | 2006-06-15 | Archer-Daniels-Midland Company | Procede de preparation et de purification d'hydroxymethyl furaldehyde et de derives |
WO2013102911A1 (fr) * | 2012-01-03 | 2013-07-11 | Council Of Scientific & Industrial Research | Procédé de conversion chimique de la cellulose extraite d'une biomasse aromatique en hydroxyméthyl furfural |
-
2015
- 2015-07-24 FR FR1557052A patent/FR3039150B1/fr not_active Expired - Fee Related
-
2016
- 2016-07-19 JP JP2018502816A patent/JP2018526342A/ja active Pending
- 2016-07-19 KR KR1020187002190A patent/KR20180034422A/ko unknown
- 2016-07-19 US US15/747,343 patent/US10239852B2/en not_active Expired - Fee Related
- 2016-07-19 CN CN201680043452.5A patent/CN108137524A/zh active Pending
- 2016-07-19 WO PCT/EP2016/067126 patent/WO2017016924A1/fr unknown
- 2016-07-19 EP EP16741608.0A patent/EP3325458A1/fr not_active Withdrawn
- 2016-07-19 BR BR112018000195A patent/BR112018000195A2/pt not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006063220A2 (fr) * | 2004-12-10 | 2006-06-15 | Archer-Daniels-Midland Company | Procede de preparation et de purification d'hydroxymethyl furaldehyde et de derives |
WO2013102911A1 (fr) * | 2012-01-03 | 2013-07-11 | Council Of Scientific & Industrial Research | Procédé de conversion chimique de la cellulose extraite d'une biomasse aromatique en hydroxyméthyl furfural |
Non-Patent Citations (3)
Title |
---|
FLORIAN ILGEN ET AL: "Conversion of carbohydrates into 5-hydroxymethylfurfural in highly concentrated low melting mixtures", GREEN CHEMISTRY, vol. 11, no. 12, 1 January 2009 (2009-01-01), pages 1948, XP055164377, ISSN: 1463-9262, DOI: 10.1039/b917548m * |
HÉCTOR QUIROZ-FLORENTINO ET AL: "Total synthesis of the natural succinate derivative of 5-(hydroxymethyl)furfural isolated from the Noni fruit ( Morinda citrifolia )", NATURAL PRODUCT RESEARCH, vol. 23, no. 14, 20 September 2009 (2009-09-20), GB, pages 1355 - 1362, XP055251381, ISSN: 1478-6419, DOI: 10.1080/14786410903040477 * |
KAWAMOTO ET AL: "Inhibition of acid-catalyzed depolymerization of cellulose with boric acid in non-aqueous acidic media", CARBOHYDRATE RESEARCH, PERGAMON, GB, vol. 343, no. 2, 7 November 2007 (2007-11-07), pages 249 - 255, XP022420337, ISSN: 0008-6215, DOI: 10.1016/J.CARRES.2007.11.004 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3076554A1 (fr) * | 2018-01-10 | 2019-07-12 | IFP Energies Nouvelles | Procede de production de 5-hydroxymethylfurfural |
WO2019137810A1 (fr) | 2018-01-10 | 2019-07-18 | IFP Energies Nouvelles | Procede de production de 5-hydroxymethylfurfural |
CN111770916A (zh) * | 2018-01-10 | 2020-10-13 | Ifp 新能源公司 | 用于合成5-羟甲基糠醛的方法 |
JP2021510371A (ja) * | 2018-01-10 | 2021-04-22 | イエフペ エネルジ ヌヴェルIfp Energies Nouvelles | 5−ヒドロキシメチルフルフラールの合成プロセス |
US11261168B2 (en) | 2018-01-10 | 2022-03-01 | IFP Energies Nouvelles | Process for synthesizing 5-hydroxymethylfurfural |
Also Published As
Publication number | Publication date |
---|---|
FR3039150B1 (fr) | 2017-07-28 |
US20180370937A1 (en) | 2018-12-27 |
KR20180034422A (ko) | 2018-04-04 |
CN108137524A (zh) | 2018-06-08 |
JP2018526342A (ja) | 2018-09-13 |
FR3039150A1 (fr) | 2017-01-27 |
US10239852B2 (en) | 2019-03-26 |
EP3325458A1 (fr) | 2018-05-30 |
BR112018000195A2 (pt) | 2018-09-11 |
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