99%| A1458588|Formula:C6H6O3|Molecular Weight:126.1150000+ products instock " />
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5-Hydroxymethylfurfural (5-HMF) is an important bio-sourced intermediate, formed from carbohydrates such as glucose or fructose and used for production of fuels and chemical intermediates.
Synonyms: 2-Hydroxymethyl-5-furfural; 2-Formyl-5-hydroxymethylfuran; 5-HMF-AesRx
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Engineering an All-Biobased Solvent- and Styrene-Free Curable Resin
Afewerki, Samson ; Edlund, Ulrica ;
Abstract: The sustainable production of polymers and materials derived from renewable feedstocks such as biomass is vital to addressing the current climate and environmental challenges. In particular, finding a replacement for current widely used curable resins containing undesired components with both health and environmental issues, such as bisphenol-A and styrene, is of great interest and vital for a sustainable society. In this work, we disclose the preparation and fabrication of an all-biobased curable resin. The devised resin consists of a polyester component based on fumaric acid, itaconic acid, 2,5-furandicarboxylic acid, 1,4-butanediol, and reactive diluents acting as both solvents and viscosity enhancers. Importantly, the complete process was performed solvent-free, thus promoting its industrial applications. The cured biobased resin demonstrates very good thermal properties (stable up to 415°C), the ability to resist deformation based on the high Young's modulus of ~775 MPa, and chem. resistance based on the swelling index and gel content. We envision the disclosed biobased resin having tailorable properties suitable for industrial applications.
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Keywords: curable resin ; biobased ; catalysis ; renewable feed-stock ; biomass ; environmental challenges
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Porous dendritic BiSn electrocatalysts for hydrogenation of 5-hydroxymethylfurfural
Piao, Guangxia ; Yoon, Sun Hee ; Cha, Hyun Gil ; Han, Dong Suk ; Park, Hyunwoong ;
Abstract: The electrocatalytic hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is an alternative to conventional heterogeneous catalysis with H2 at high temperatures and pressures. Although Ag is the most representative electrocatalyst, it works only under limited conditions. This study synthesizes highly porous dendritic Bi, Sn, and BiSn electrocatalysts using an in situ generated hydrogen bubble template. Density functional theory computations on the adsorption energy and elementary hydrogenation reaction steps of HMF predict the superiority of Bi to Sn and the intermediate behavior of BiSn between Bi and Sn. The dendritic BiSn catalyst generates a current density of ~144 mA cm?2 at a faradaic efficiency (FE) of ~100% for BHMF production at pH ~ 7 (corresponding to the BHMF production rate of ~2.7 mmol h?1 cm?2) in prolonged electrolysis. Considering the material cost (
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CAS No. : | 67-47-0 |
Formula : | C6H6O3 |
M.W : | 126.11 |
SMILES Code : | C1=C(OC(=C1)C=O)CO |
Synonyms : |
2-Hydroxymethyl-5-furfural; 2-Formyl-5-hydroxymethylfuran; 5-HMF-AesRx
|
MDL No. : | MFCD00003234 |
InChI Key : | NOEGNKMFWQHSLB-UHFFFAOYSA-N |
Pubchem ID : | 237332 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H332-H335 |
Precautionary Statements: | P261-P280-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72 %Spectr. | at 100℃; for 10 h; | 1.8 g of sucrose,0.271 g of GeCl4, 0.091 g of BBr3, and 20 mL of n-propanol were added to 50 mL of a polyTetrafluoroethylene-lined stainless steel reactor,Heated to l00 ° C,The reaction was carried out at that temperature for 10 h. Filtration,To remove unreacted sucrose and other insoluble impurities,The solvent was removed by rotary evaporation,2 mL H20 was added and the organic phase was extracted with methyl isobutyl ketone,The resulting organic phase was rotary evaporated to a high purity furan derivative,The isolated yield was 83percent. The qualitative analysis of the reaction products was carried out by gas chromatography-mass spectrometry (GC-MS)And with the standard material (HMF,5-propoxymethylfurfural and propyl propionate) in gas chromatography (GC) were compared and confirmed. Quantitative analysis of the yield distribution of different furan derivatives was confirmed by 1H NMR,The product distribution results are:5-propoxymethylfurfural was 72percent, HMF was 9percentPropyl propionate was 19percent |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With nicotinamide adenine dinucleotide; sodium hydroxide; In aq. phosphate buffer; at 35℃; for 0.5h;pH 8.5;Enzymatic reaction; | ALD-003 (5mg), NOX-009 or NOX-001 (5mg) and NAD or NADP (2Omol% based upon the amount of ALD-003) was added to 0.5mL 0.25M KPi (pH 8.5). The pH was adjusted to pH 8.5 with 1M NaOH. 10mM DFF or HMF was added and the reaction was left in ashaking incubator at 35C. After a specified time the reaction was quenched with 1 M HCI, centrifuged and analysed by RP-HPLC. The results are found in Tables 5, 6, and 7A. Reaction Conditions: 0.SmL KPi 0.25M pH 8.5, 5mg CFE, 2Omol% cofactor, 5mg NOX,10mM Substrate, 35C, reaction time 30 minutes. |
99% | With oxygen; sodium hydroxide; In water; at 20℃; | 0.2g of 5-hydroxymethylfurfural,0.05g Ag-PVP/ZrO2 catalyst (Ag:PVP=1:0.5 (molar ratio), 2.5% load),0.126g NaOH, 50mL water was added to a 150mL three-necked flask,And oxygen is introduced, the oxygen flow rate is 60 mL/min, and the reaction is carried out at a temperature of 20 C.Real-time sampling,The product was determined by high performance liquid chromatography for the content of 5-hydroxymethylfurfural and 5-hydroxymethylnonanoic acid.When the reaction is 12h,The conversion rate of 5-hydroxymethylfurfural is 99%.Yield of 5-hydroxymethyl-furoic acid 99%The selectivity is 100%. |
92% | With oxygen; sodium hydroxide; In water; at 80℃; under 3750.38 Torr; for 12h;Autoclave; Green chemistry; | Take 0.317 g of HMF, 2 g of NaOH (20%) and 3 ml of water into the autoclave. The reaction vessel was charged with 10 ml of polytetrafluoroethylene lined autoclave with 0.30 g Pt / NaY (Pt lwt% As the catalyst, the program temperature to 80 C, filled with 0.5MPa oxygen, the reaction 12 hours, the reaction process continue to add oxygen to ensure that the reaction at constant temperature and constant pressure. The reaction product was centrifuged and the supernatant was removed and analyzed using HPLC. The results showed that the conversion rate of HMF was 100% and the yield of HMFA was 92%. The reaction results are shown in Table 1. |
With oxygen; sodium carbonate; In water; at 20 - 50℃; for 2h; | Catalytic Reaction Of HMF To FDCA For this reaction, Na2C03 was used as the base. 1 g of extracted HMF was first dissolved in 5 g of water. The Na2C03 was separately prepared by dissolving Na2C03 in water. The oxidation catalyst was then added follow by the HMF solution at ambient room temperature. With oxygen gas bubbling, the solution was first heated to 50C for 2 hours, and HMF was fully converted to HFCA. After that, the reaction was heat to 95C and kept for 7 hour. The pH of the aqueous solution was then adjusted to 1 and FDCA was precipitated from the solution. The precipitate was filtered and washed with ethanol. | |
2.74 g | With 4% Au/TiO2; oxygen; sodium hydroxide; In water; at 70℃; for 7h;pH 10; | 10 g of HMF, 150 g of water, and 1 g of catalyst (4% Au/TiO2) were added into a round bottom bottle (250 mL) and then heated to 70 C. Air under atmosphere pressure was introduced into the liquid in the flask. The pH value of the above reaction was controlled to 10 by adding a sodium hydroxide aqueous solution into the flask. The reaction was continued for 7 hours to obtain a crude aqueous solution. The crude aqueous solution was extracted by 200 mL of ethyl acetate two times, and the aqueous phase of the extractions was collected by a separatory funnel. The collected aqueous phase was titrated by concentrated hydrochloric acid (HCl) until its pH value reached 3. The acidified aqueous phase was extracted by 200 mL of ethyl acetate two times, and the organic phase of the extractions was collected. The collected organic phase was vacuumed concentrated to obtain 2.74 g of solid, which was 5-hydroxymethyl-2-furoic acid (HMFCA). The above reaction is shown in Formula 8. The product of Formula 8 had NMR spectra as below: 1H NMR (400 MHz, d-DMSO): 13.08 (br, 1H), 7.14 (d, 1H, J=3.4 Hz), 6.45 (d, 1H, J=3.4 Hz), 5.59 (s, 1H), 4.44 (s, 2H); 13C NMR (100 M Hz, d-DMSO): 160.1, 159.8, 144.4, 119.0, 109.4, 56.2. |
2.74g | With gold on titanium oxide; oxygen; sodium hydroxide; In water; at 70℃; under 760.051 Torr; for 7h;pH 10; | 10 g of HMF,150 g of water,And 1 g of 4% Au / TiO2 catalyst250 mL of a round bottom flask,Heated to 70 C,And air was introduced under normal pressure.The pH of the reaction was then controlled to 10 with the addition of aqueous sodium hydroxide,After 7 hours of continuous reaction, an aqueous solution of the crude product was obtained.The crude aqueous solution was added to 200 mL of ethyl acetate for extraction twice,The water layer was taken in a separatory funnel.The aqueous layer was titrated with concentrated hydrochloric acid (HCl) until the pH was 3.After extraction twice with 200 mL of ethyl acetate, the organic layer was taken.The organic layer was concentrated under reduced pressure to give 2.74 g of a solid,5-hydroxymethyl-2-furoic acid (HMFCA).The above reaction is shown in Formula 8 below. |
With sodium hydroxide; In water; at 30℃; under 2250.23 Torr; for 5h; | The Au / MgO (Au0.5 wt%) catalyst, 1 mmol of 5-hydroxymethylfurfural, NaOH, 10 ml of water was charged to a stainless steel autoclave with a Teflon-lined internal metal, 5-hydroxymethylfurfural: NaOH = 0.015: 1: 4 (mol: mol: mol).Using automatic temperature control program temperature to the reaction temperature of 30 C, adding 0.3MPa oxygen, reaction 5 hours, the reaction process to maintain the same pressure.The reaction product was analyzed by HPLC. | |
95%Chromat. | With recombinant Escherichia coli cells expressing 3-succinoylsemialdehyde-pyridine dehydrogenase from Comamonastestosteroni SC1588; In aq. phosphate buffer; at 30℃; for 5h;pH 7;Enzymatic reaction; | General procedure: Typically, 4 mL of phosphate buffer (0.2 M, pH 7) containing 50mMFF and 50 mg (cell wet weight) per mL microbial cells was incubated at30 C and 160 r/min. Aliquots were withdrawn from the reaction mixturesat specified time intervals and diluted with the correspondingmobile phase prior to HPLC analysis. The conversion was defined as theratio of the consumed substrate amount to the initial substrate amount(in mol). The yield was defined as the ratio of the formed productamount to the theoretical value based on the initial substrate amount(in mol). The selectivity was defined as the ratio of the formed productamount to the total amount of all products (in mol). All the experimentswere conducted at least in duplicate, and the values were expressed asthe means ± standard deviations. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9%; 60%; 7% | With iron(II) phthalocyanine; In aq. phosphate buffer; at 37 - 80℃; for 16.0833h;pH 7; | HMF (100 mM) was added to KPi buffer (500 mM pH 7.0). GOase M35 (103p1 of3.3mg/mL), PaoABC (ipI of 28.9mg/mL) and a metal complex (see Table 4) were added at 37 00 and the pH was continuously adjusted with NaHCO3 for a period of 16 hours. The reaction was heated to 80 00 for 5 minutes and left to cool. The solution containing denatured protein was centrifuged and the supernatant removed and analysed by RP20 HPLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water;phosphoric acid; at 50 - 95℃; for 0.25 - 0.75h;pH 1.75 - 3.75; | Figure 4, from a second laboratorial work, is a TLC - Thin Layer Chromatography on silicagel 60 (Merck) developed with the mixture isopropanol : ethyl acetate : water 5:1 :2 as mobile phase and with partial runs of 1/3, 2/3, and 3/3 of the front line and developed with orcinol : sulfuric acid : methanol at 1000C for 5 minutes. This figure illustrates the profile of FOS - Fructooligosaccharides when one hydrolyzes purified inulin from dahlia roots (5g%) with phosphoric acid at pH = 2.5 at 850C during 15 minutes (15), 30 minutes (30), and 45 minutes (45), indicating that the modulation of a single kinetic parameter - time of hydrolysis - already allows to govern the quantitative relation of FOS > fructose (cases 15 and 30) or the opposite (FOS < fructose; 45). A similar strategy for FOS > fructose may also be governed by the other parameters (pH itself or temperature of hydrolysis), as shown for hydrolysis of inulin with phosphoric or citric acids at pHs from 1.75 to 3.75 in the range of 5O0C to 95oC (as better explained in Figure 5). In Figure 4, (f) and (g) denotes for free fructose and glucose, respectively. GP refers to the Degree of Polymerization. It is remarkable that phosphoric or citric hydrolyses of inulin may be effectively addressed <n="27"/>to the preferential preparation of FOS - Fructooligosaccharides since when addressed to a higher fructose content (lane 45), some amount of the co-product HMF - hydroxymethylfurfural turns clearly visible in the front zone of the chromatogram. Its companion spot most probably is a DFA (difructose anhydride).; Figure 5 is a bar graphic comparing the effect of the kinetic parameters such as temperature and time of hydrolysis once fixed the hidrogenionic potential at pH = 2.5 and their respective capacities for the modulation on the qualitative nature of the products from the hydrolyses of dahlia inulin with phosphoric or citric acids when the substrate is used at a concentration of 5g%. According to the intended innovation in this patent request - the preferential production of FOS or FrutoOligoSaccharides - is obviously that, for each range of temperature, namely, 750C, 850C ou 950C, either in the phosphoric or in the citric hydrolyses, the formation of FOS is preferential in (8x2 =) 16 assays, except for those two - at 950C and during 25 minutes - where fructose shows predominance with respect to FOS. Incidentally, those two exceptional conditions - which are not the scope of this patent request - also led to the formation of some HMF - hydroxymethylfurfural - undesirable in a inulin hydrolysis, with the attenuating condition that a less expensive practice as activated charcoal is able to remove the contaminant HMF. Concerning the reaction yield reported to the initial inulin input, the diluted phosphoric acid guarantees in the times of 25 min at 850C and of 15 min at 950C percentages of hydrolyses up to 80%, being the most of the products - 76% and 63%, respectively - FOS or frutooligosaccharides and being the remaining fructose since HMF is no longer detected under these conditions of hydrolysis. The same approach is attained with citric acid although with somewhat reduced yields - 64% or 76%, but even so FOS correspond to 78% and 74% of the hydrolysis products.; Figure 6 derives from another practical example of laboratory work, namely a high performance liquid chromatography or HPLC in a column of 10 micra microparticles of silica gel derivatized with amino groups and provided by Spectraphysics. Twenty microliters of a citric hydrolyzate of inulin at 10% obtained at pH 2.5 during 5 or 15 minutes at 850C were applied to the column and elution proceeded with 70% acetonitrile at a 1 mL/min flow rate and the monitoring was carried out with DRI- differential refraction index. It is shown that in both conditions <n="28"/>- 5 and 15 minutes - inulin is converted, by citric acid, into a family of FOS - FructoOligoSaccharides with DP - Degree of Polymerization - 3 to 18 or more (considering the analytical capacity of the referred column), still emphazing that fructose, with respect to FOS concentration, contributes with a maximum of 25% and a minimum of 5%.; Figure 7, resulting from another practical laboratory work, is also - like Figure 6 - a HPLC but carried out with samples arising from phosphoric acid hydrolyses under the same conditions of those described in Figure 6. The qualitative profiles for FOS are quite similar in both figures. In 8 of 9 assays, FOS predominates. In the nineth - 25 minutes of hydrolysis at higher temperature - FOS and fructose contents are more or less equivalent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water;citric acid; at 50 - 95℃; for 0.25 - 0.75h;pH 1.75 - 3.75; | Figure 4, from a second laboratorial work, is a TLC - Thin Layer Chromatography on silicagel 60 (Merck) developed with the mixture isopropanol : ethyl acetate : water 5:1 :2 as mobile phase and with partial runs of 1/3, 2/3, and 3/3 of the front line and developed with orcinol : sulfuric acid : methanol at 1000C for 5 minutes. This figure illustrates the profile of FOS - Fructooligosaccharides when one hydrolyzes purified inulin from dahlia roots (5g%) with phosphoric acid at pH = 2.5 at 850C during 15 minutes (15), 30 minutes (30), and 45 minutes (45), indicating that the modulation of a single kinetic parameter - time of hydrolysis - already allows to govern the quantitative relation of FOS > fructose (cases 15 and 30) or the opposite (FOS < fructose; 45). A similar strategy for FOS > fructose may also be governed by the other parameters (pH itself or temperature of hydrolysis), as shown for hydrolysis of inulin with phosphoric or citric acids at pHs from 1.75 to 3.75 in the range of 5O0C to 95oC (as better explained in Figure 5). In Figure 4, (f) and (g) denotes for free fructose and glucose, respectively. GP refers to the Degree of Polymerization. It is remarkable that phosphoric or citric hydrolyses of inulin may be effectively addressed <n="27"/>to the preferential preparation of FOS - Fructooligosaccharides since when addressed to a higher fructose content (lane 45), some amount of the co-product HMF - hydroxymethylfurfural turns clearly visible in the front zone of the chromatogram. Its companion spot most probably is a DFA (difructose anhydride).; Figure 5 is a bar graphic comparing the effect of the kinetic parameters such as temperature and time of hydrolysis once fixed the hidrogenionic potential at pH = 2.5 and their respective capacities for the modulation on the qualitative nature of the products from the hydrolyses of dahlia inulin with phosphoric or citric acids when the substrate is used at a concentration of 5g%. According to the intended innovation in this patent request - the preferential production of FOS or FrutoOligoSaccharides - is obviously that, for each range of temperature, namely, 750C, 850C ou 950C, either in the phosphoric or in the citric hydrolyses, the formation of FOS is preferential in (8x2 =) 16 assays, except for those two - at 950C and during 25 minutes - where fructose shows predominance with respect to FOS. Incidentally, those two exceptional conditions - which are not the scope of this patent request - also led to the formation of some HMF - hydroxymethylfurfural - undesirable in a inulin hydrolysis, with the attenuating condition that a less expensive practice as activated charcoal is able to remove the contaminant HMF. Concerning the reaction yield reported to the initial inulin input, the diluted phosphoric acid guarantees in the times of 25 min at 850C and of 15 min at 950C percentages of hydrolyses up to 80%, being the most of the products - 76% and 63%, respectively - FOS or frutooligosaccharides and being the remaining fructose since HMF is no longer detected under these conditions of hydrolysis. The same approach is attained with citric acid although with somewhat reduced yields - 64% or 76%, but even so FOS correspond to 78% and 74% of the hydrolysis products.; Figure 6 derives from another practical example of laboratory work, namely a high performance liquid chromatography or HPLC in a column of 10 micra microparticles of silica gel derivatized with amino groups and provided by Spectraphysics. Twenty microliters of a citric hydrolyzate of inulin at 10% obtained at pH 2.5 during 5 or 15 minutes at 850C were applied to the column and elution proceeded with 70% acetonitrile at a 1 mL/min flow rate and the monitoring was carried out with DRI- differential refraction index. It is shown that in both conditions <n="28"/>- 5 and 15 minutes - inulin is converted, by citric acid, into a family of FOS - FructoOligoSaccharides with DP - Degree of Polymerization - 3 to 18 or more (considering the analytical capacity of the referred column), still emphazing that fructose, with respect to FOS concentration, contributes with a maximum of 25% and a minimum of 5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
19%; 10%; 35%; 20%; 8% | With dihydrogen peroxide;methyltrioxorhenium(VII); In dichloromethane; water; acetonitrile; at 20℃; | Comparative examples 1 to 3: Oxidation of 5-hydroxymethyl furfural in homogeneous conditions; 5-hydroxymethyl furfural (HMF) was oxidized with 10 equivalents of hydrogen peroxide (35percent by weight in aqueous solution) in the presence of methyltrioxo rhenium in an amount of 5percent by weight of HMF, at a temperature about 200C during 24 to 48 hours, until the conversion of furfural was complete, in various solvents. The results of the reactions are summarized in Table 1 below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23%; 6%; 11%; 16%; 29% | With dihydrogen peroxide;methyltrioxorhenium(VII); In ethanol; water; at 20℃; | Comparative examples 1 to 3: Oxidation of 5-hydroxymethyl furfural in homogeneous conditions; 5-hydroxymethyl furfural (HMF) was oxidized with 10 equivalents of hydrogen peroxide (35percent by weight in aqueous solution) in the presence of methyltrioxo rhenium in an amount of 5percent by weight of HMF, at a temperature about 200C during 24 to 48 hours, until the conversion of furfural was complete, in various solvents. The results of the reactions are summarized in Table 1 below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
7%; 90% | With bis-acetylacetonyl vanadium (II); In aq. phosphate buffer; at 37 - 80℃; for 16.0833h;pH 7; | HMF (100 mM) was added to KPi buffer (500 mM pH 7.0). GOase M35 (103p1 of3.3mg/mL), PaoABC (ipI of 28.9mg/mL) and a metal complex (see Table 4) were added at 37 00 and the pH was continuously adjusted with NaHCO3 for a period of 16 hours. The reaction was heated to 80 00 for 5 minutes and left to cool. The solution containing denatured protein was centrifuged and the supernatant removed and analysed by RP20 HPLC. |
With sodium carbonate; at 100℃; under 30003 Torr; for 0.1h;pH 10.12; | Experimental Conditions The HMF having 95% purity was supplied by Interchim. The method of the invention was implemented in a discontinuous reactor under pressure in a 300 mL autoclave equipped with magnetically driven gas-inducing agitator. Heating was ensured by a heating collar connected to a PID controller (proportional integral derivative). A sampling gate allowed the taking of a sample from the reaction medium via an immersed tube, allowing the monitoring of the progress of the reaction over time. The samples were analysed by HPLC chromatography with two RID detectors (Refractive Index Detector) and PDA (Photodiode array) (ICE-Coragel 107H column, eluting with 10 mM H2SO4). Total Organic Carbon (TOC) in solution was also analysed using a TOC analyser and the value measured was compared with the mass balance (MB) calculated by HPLC. The reactor was charged with 150 mL of 100 mM aqueous HMF solution (2 g), a weight of catalyst corresponding to a HMF/Pt molar ratio of 100, and the desired amount of base in the form of NaOH (comparative example), NaHCO3, KHCO3, Na2CO3 or K2CO3 expressed as base/HMF molar ratio. Air was added at a pressure of 40 bar and the reactor heated to 100 C. The influence of the Bi/Pt ratio was also examined in the presence of Na2CO3 (Na2CO3/HMF=2). The same trend was observed when comparing a series of bimetallic catalysts having molar ratios varying between 0.07 and 1. The results are grouped together in Tables 11 to 15. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86%; 6.6%; 7.3% | With bis-acetylacetonyl vanadium (II); In aq. phosphate buffer; at 37 - 80℃; for 16.0833h;pH 7; | HMF (100 mM) was added to KPi buffer (500 mM pH 7.0). GOase M35 (103p1 of3.3mg/mL), PaoABC (ipI of 28.9mg/mL) and a metal complex (see Table 4) were added at 37 00 and the pH was continuously adjusted with NaHCO3 for a period of 16 hours. The reaction was heated to 80 00 for 5 minutes and left to cool. The solution containing denatured protein was centrifuged and the supernatant removed and analysed by RP20 HPLC. |
With platinum on carbon; water-d2; oxygen; at 100℃; under 75007.5 Torr; for 4h;Autoclave; | l-b Catalyst screening experiments: Catalyst screening was carried out in a series of single experiments designated "Screen 1 " to "Screen 7". In each single experiment "Screen 1 " to "Screen 7" the organic reactant compound HMF (compound of Formula (II)) was in parts catalytically converted by means of at least one heterogeneous platinum catalyst (see Tables 1 and 2, below) into FDCA (compound of formula (I)). The general experimental procedure for each screening experiment of "Screen 1 " to "Screen 7" was as follows: In a first step, an aqueous reactant mixture was prepared by filling a specific amount of deuterated water (D20, 99,9 atom%, Sigma Aldrich (151882)) and a specific amount of HMF (99+%, Sigma Aldrich (W501808)) into a steel autoclave reactor (inner volume 60 ml or 90 ml, respectively, for exact information see Table 2, below). In case a steel autoclave reactor with an inner volume of 60 ml was used the amounts of HMF and D20 were as follows: D20: 18,0 g, HMF: 2,0 g (corresponding to 15,9 mmol as starting amount of HMF). In case a steel autoclave reactor with an inner volume of 90 ml was used the amounts of HMF and D20 were as follows: D20: 27,0 g, HMF: 3,0 g (corresponding to 23,8 mmol as starting amount of HMF). The starting concentration C0[HMF] of HMF in each aqueous reactant mixture was 10 % by weight, based on the total mass of the aqueous reactant mixture (total mass of deuterated water and HMF). The respective amount of solid heterogeneous catalyst as stated in Table 2 was added to the respective aqueous reactant mixture and, thus, a reaction mixture comprising deuterated water, HMF, and the heterogeneous catalyst was obtained. After adding the specific amount of heterogeneous catalyst the obtained reaction mixture appeared as a deep black slurry, the black color apparently caused by the black solid particles of the heterogeneous catalyst. The molar ratio of substrate to metal of the heterogeneous catalyst (HMF : Pt) was approximately 100 : 1. In a second step, the filled reactor was tightly sealed and pressurized with synthetic air (total pressure 100 bar, Oxygen (as part of the synthetic air) : HMF ratio is approximately 2,25 : 1 ) to obtain conditions for catalytic conversion. The present reaction mixture was heated to a temperature of 100C while stirring at 2000 rpm. After reaching 100C this temperature was maintained for 4 or 20 hours, respectively, (see Table 2 "Reaction time" for exact information) while continuing stirring the heated and pressurized reaction mixture during the reaction time. As a result, a first product suspension comprising FDCA in solid form and the heterogeneous catalyst in solid form was formed. | |
With sodium carbonate; at 100℃; under 30003 Torr; for 0.33h;pH 9.10; | Experimental Conditions The HMF having 95% purity was supplied by Interchim. The method of the invention was implemented in a discontinuous reactor under pressure in a 300 mL autoclave equipped with magnetically driven gas-inducing agitator. Heating was ensured by a heating collar connected to a PID controller (proportional integral derivative). A sampling gate allowed the taking of a sample from the reaction medium via an immersed tube, allowing the monitoring of the progress of the reaction over time. The samples were analysed by HPLC chromatography with two RID detectors (Refractive Index Detector) and PDA (Photodiode array) (ICE-Coragel 107H column, eluting with 10 mM H2SO4). Total Organic Carbon (TOC) in solution was also analysed using a TOC analyser and the value measured was compared with the mass balance (MB) calculated by HPLC. The reactor was charged with 150 mL of 100 mM aqueous HMF solution (2 g), a weight of catalyst corresponding to a HMF/Pt molar ratio of 100, and the desired amount of base in the form of NaOH (comparative example), NaHCO3, KHCO3, Na2CO3 or K2CO3 expressed as base/HMF molar ratio. Air was added at a pressure of 40 bar and the reactor heated to 100 C. The influence of the Bi/Pt ratio was also examined in the presence of Na2CO3 (Na2CO3/HMF=2). The same trend was observed when comparing a series of bimetallic catalysts having molar ratios varying between 0.07 and 1. The results are grouped together in Tables 11 to 15. |
With nicotinamide adenine dinucleotide phosphate; In aq. phosphate buffer; at 37℃; for 2h;pH 7;Enzymatic reaction; | Reaction Conditions: HMF (10mM), KRED (089) (7.5mg), 0.SmL KPi Buffer (pH x), and NOX-1 and NADP as defined in Table 7B were reacted at 37C for 2 hours. A sample was quenched with 1 M HCI, centrifuged and analysed by RP-HPLC. The results from thereaction can be seen in Table 7B.Using lOmol% of NADP (relative to the amount of HMF used) and 5mg NOX-1 provided the highest conversion of HMF to 2,5-FDCA. Reducing the amount of NADP and NOX-1 lead to a lower conversion of HMF to HMFCA. | |
With nicotinamide adenine dinucleotide phosphate; In aq. phosphate buffer; at 37℃; for 2h;pH 7;Enzymatic reaction; | Reaction Conditions: HMF (10mM), KRED (089) (7.5mg), 0.SmL KPi Buffer (pH x), and NOX-1 and NADP as defined in Table 7B were reacted at 37C for 2 hours. A sample was quenched with 1 M HCI, centrifuged and analysed by RP-HPLC. The results from thereaction can be seen in Table 7B.Using lOmol% of NADP (relative to the amount of HMF used) and 5mg NOX-1 provided the highest conversion of HMF to 2,5-FDCA. Reducing the amount of NADP and NOX-1 lead to a lower conversion of HMF to HMFCA. | |
With nicotinamide adenine dinucleotide phosphate; In aq. phosphate buffer; at 37℃; for 2h;pH 7;Enzymatic reaction; | Reaction Conditions: HMF (10mM), KRED (089) (7.5mg), 0.SmL KPi Buffer (pH x), and NOX-1 and NADP as defined in Table 7B were reacted at 37C for 2 hours. A sample was quenched with 1 M HCI, centrifuged and analysed by RP-HPLC. The results from thereaction can be seen in Table 7B.Using lOmol% of NADP (relative to the amount of HMF used) and 5mg NOX-1 provided the highest conversion of HMF to 2,5-FDCA. Reducing the amount of NADP and NOX-1 lead to a lower conversion of HMF to HMFCA. | |
7.67%Chromat.; 18.1%Chromat.; 73.67%Chromat. | With platinum on activated charcoal; sodium hydroxide; In 1-methyl-pyrrolidin-2-one; water; at 80℃; under 16501.7 Torr; for 0.5h;Flow reactor; | 1.) NMP/NaOH/Pt-C/air/22bar/90Ci) Oxidation 1 - inNMP, Pt-c, 17 bar and 80C, NaOHThe starting solution A is prepared by dissolving 5-Hydroxymethylfurfural (99%) in 95gNMP (99,5%, Sigma Aldrich) and 5g deionized water. The starting solution B is a 15%NaOH solution, prepared from 150.41 g NaOH and 850.1 8g deionized water.In a continuous flow plant, solution A and solution B are contacted in a 1/16? t-piece. The flow rate for solution A is 0.08 ml/min, and for solution B 0.06 ml/min. The mixture obtained is directly contacted with 125 ml/min air flow, before the mixture enters the actual reactor. In this case the reactor was a trickle bed reactor using platinum on activated carbon as catalyst. The double jacketed reactor is heated to 80C and provides a residence time of 30 minutes for the given flow rates. The whole system is pressurized to 22 bar with a pressure maintaining valve.The reaction mixture obtained in this step contains no HMF. The oxidation product mixture contains, according to HPLC analysis, FDCA: 73.67%, HMFCA: 18.10%, FFCA: 7.67%, DFF: 0.41% and 0.15% unknown oxidation products. Additionally, a small amount of dark, solid material is yielded using this procedure, leading to a reduced lifetime cycle of the catalyst fixed bed.ii.) Extraction with ethyl acetateThe reaction mixture (20.4m1) collected from the first oxidation step was extracted six times using 20 ml ethyl acetate per cycle to remove NMP. The HPLC chromatogram showed noloss of the acids in the aqueous phase after this procedure. The DFF was transferred completely to the organic phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89%; 5% | With sodium hydroxide; In water; at 30℃; under 7500.75 Torr; for 4h; | The Au / Mg (OH)2(1 wt%) catalyst, 2 mmol of 5-hydroxymethylfurfural, NaOH and 10 mL of water were charged into a stainless steel autoclave equipped with a polytetrafluoroethylene liner containing 5-hydroxymethylfurfural: NaOH = 0.01: 1 : 4 (mol: mol: mol).Using automatic temperature control program temperature to the reaction temperature of 30 C, adding 1MPa oxygen, reaction for 4 hours, the reaction process to maintain the same pressure.The reaction product was analyzed by HPLC. |
76%; 12% | With oxygen; potassium hydroxide; In water; at 60℃; under 2250.23 Torr; for 6h;Autoclave; Green chemistry; | Take 0.317 grams of HMF, 2.8 grams of Kappa0Eta (20%), 3 ml of water into the reactor, the reaction vessel containing 10 ml of poly Tetrafluoroethylene-lined high-pressure reactor, take 0.30 g Au / HY (Au2wt%) as a catalyst, the program heated to 60 C, filling 0.3MPa oxygen, the reaction 6 hours, the reaction process continue to add oxygen to ensure that the reaction at constant temperature and constant pressure. reaction product After centrifugation, go to the supernatant and analyze with HPLC. The HMF conversion was 100%, the yield of HMFA was 76% FDA yield of 12%, the reaction results in Table 1. |
26%; 73% | With vanadium(V) oxide; In aq. phosphate buffer; at 37 - 80℃; for 16.0833h;pH 7; | HMF (100 mM) was added to KPi buffer (500 mM pH 7.0). GOase M35 (103p1 of3.3mg/mL), PaoABC (ipI of 28.9mg/mL) and a metal complex (see Table 4) were added at 37 00 and the pH was continuously adjusted with NaHCO3 for a period of 16 hours. The reaction was heated to 80 00 for 5 minutes and left to cool. The solution containing denatured protein was centrifuged and the supernatant removed and analysed by RP20 HPLC. |
60%; 33% | With bis-acetylacetonyl vanadium (II); In aq. phosphate buffer; at 37 - 80℃; for 16.0833h;pH 7; | HMF (100 mM) was added to KPi buffer (500 mM pH 7.0). GOase M35 (103p1 of3.3mg/mL), PaoABC (ipI of 28.9mg/mL) and a metal complex (see Table 4) were added at 37 00 and the pH was continuously adjusted with NaHCO3 for a period of 16 hours. The reaction was heated to 80 00 for 5 minutes and left to cool. The solution containing denatured protein was centrifuged and the supernatant removed and analysed by RP20 HPLC. |
59.4%; 40.6% | With oxygen; sodium hydroxide; In water; at 24.84℃; for 6h; | The HMF oxidation reaction was carried out in a three-neck flask with an attached glass reflux condenser under oxygen flow (Figure 2). In each experiment, the reactor was filled with 1.0mmol of HMF and 5.0mmol of NaOH in 10mL of water. Then, 0.1 g of M/RGO (M = Pd, Rh, Ru, or Pt) was added to the reactor, and oxygen was introduced at a flow rate of 50mL min-1 with stirring under atmosphere pressure. After reaction, the catalyst was filtered off before the high-performance liquid chromatography (HPLC) measurement (AnimexHPX-87H column from Bio-Rad Laboratories Co., Ltd., 0.5mL min-1 flow rate, 10nM H2SO4 solvent, 323 K). The products were analyzed using a refractive index (RI) detector. |
39%; 45% | With oxygen; sodium hydroxide; In water; at 60℃; under 2250.23 Torr; for 6h;Autoclave; Green chemistry; | Take 0.317 grams of HMF, 2 grams of NaOH (20%), 3 ml of water into the reactor, the reaction vessel was equipped with a 10 ml polytetrafluoroethylene lined high pressure reactor, 0.30 g Au / H x Na 1-x Y (Au 2 wt%) as a catalyst, after the program is warmed to 60 C, filled with 0.3MPa oxygen, reaction for 6 hours, during the reaction, oxygen is continuously added, ensure that the reaction is carried out at constant temperature and pressure. The reaction product was centrifuged to the supernatant, analytical using HPLC. after testing, HMF conversion rate of raw materials is 100% HMFA yield of 39%, FDA yield of 45%, the reaction results in Table 1. |
With oxygen; sodium hydroxide; In water; at 60℃; under 7500.75 Torr; for 4h;Autoclave; | The oxidation of 5-hydroxymethyl-2-furfural (HMF) was carriedout using an autoclave (Parr Instruments) reactor of 300 mLcapacity and equipped with a mechanical stirrer (0-1200 rpm) andprovision for measurement of temperature and pressure. The reactorwas charged with an aqueous solution (25 mL distilled water)containing the appropriate amount of 5-hydroxymethyl-2-furfural,base (NaOH) and catalyst (HMF/metal molar ratio = 100). The autoclavewas purged 3 times with O2 (5 bar) and then pressurized at10 bar. If not differently indicated, the temperature was increasedto 60 C and the reaction mixture was stirred at ca. 1000 rpm for4 h. At the end of the reaction, the reactor was cooled to room temperatureand the solution was filtered. Then, 4 mL of water wasadded to an aliquot of the reaction solution (1 mL) before analysiswith an Agilent Infinity 1200 liquid chromatograph equippedwith a Aminex HPX 87-H 300 mm×7.8 mm column using a0.005 M H2SO4 solution as the mobile phase. Identification of compoundswas achieved by calibration using reference commercialsamples. | |
86.39%Chromat.; 9.2%Chromat. | With disodium hydrogenphosphate; copper oxides/alumina; at 90℃; under 13501.4 Torr; for 0.166667h; | i) Oxidation 1 - inNMP, Pt-C, 17 bar and 80C, Na2HPO4The process was carried out in a comparable, scaled up continouos lab-plant setup as used inthe examples above. Starting solution A was prepared by mixing 65.6g HMF and 400.OgNMP; solution B was a 15% solution of sodium phosphate, prepared by mixing 150.OgNa2HPO4 and 850.Og of deionized water.The flow rates used in this trial were 2.86m1/min solution A, 2.14m1/min solution B and 250.Onml/min for air. Further processing parameters were 10 minutes residence time at 90C and 18 bar. The catalyst used was copper oxide on aluminium oxide.The oxidation product mixture obtained from this trial contains, according to HPLC analysis, FDCA: 9.20%, HMFCA: 86.39%, FFCA: 0.13%, DFF: 0.36% and 2.82% of HMF. About 1% are unidentified side products.ii.) Extraction with ethyl acetateNMP extraction was carried out with ethylacetate. 50m1 reaction mixture was extracted six times with 40m1 ethyl acetate in each cycle.FDCA, HMFCA and FFCA remained completely in the water phase. Also a small amount of HMF was found in the water phase (0.5% according to HPLC). DFF completely went into the organic phase and was discarded. |
21%Chromat.; 74%Chromat. | With oxygen; sodium hydrogencarbonate; In water; under 7500.75 Torr;Autoclave; Heating; | HMF (0.2 mmol), NaHCO3 (0.4 mmol), and the catalyst (25 mg) were added to a 12 mL stainless steel autoclave containing 8 mL of deionized water. The autoclave was heated to 80 C and pressurized with O2 (10 bar) under vigorous stirring (900 rpm). During the reaction, 0.1 mL sample was taken at regular intervals of about 0.5-1 hours, filtered with 0.2 mum PTFE filters, diluted with water and analyzed using a high-performance liquid chromatograph (Shimadzu LC-20AD equipped a Bio-Rad Aminex HPX-87H column). Sulfuric acid (5 mM) at 333 Kwith a flow rate of 0.55 mL min-1 was used as an eluent. Each catalyst was tested at least twice to verify the reproducibility. The reproducibility of conversion levels and yields were within 5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; at 0 - 20℃; | With reference to Scheme 1 below, 1 ml of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIm]TFSI, available from Merck) newly serving as an ionic liquid was placed in a round-bottom flask, 0.126 g (1 mmol) of 5-hydroxymethylfurfural (HMF, Compound I) was dissolved, the reaction temperature was adjusted to 0° C., and then sodium hydroxide powder (0.200 g, 5 mmol) was added thereto. Subsequently, the reaction temperature was increased to room temperature so that the reaction took place. After completion of the reaction, 20 ml of dichloromethane was added, after which the filtrate obtained via filtration, namely, the dichloromethane layer was distilled under reduced pressure, thus recovering the ionic liquid. [0057] The lump of filtered particles resulting from recovering the ionic liquid was dissolved in 2 ml of water, and then neutralized with 1 N HCl, so that the pH of the solution was adjusted to about 78. Extraction using ethyl acetate (3×50 ml) and then concentration under reduced pressure were conducted, yielding 2,5-dihydroxymethylfuran (DHMF, Compound II) as a white solid. [0058] The pH of the remaining water layer was adjusted to about 3, followed by performing extraction using ethyl acetate and then concentration under reduced pressure, yielding 5-hydroxymethylfuranoic acid (HMFA, Compound III) as a light yellow solid. The yields of the products are shown in Table 1 below. [0059] The melting point of the light yellow crystals was 239.5° C., and the light yellow crystals were analyzed to be a target compound using 1H-NMR, 13C-NMR. The analytic data was as follows. [0060] HMFA: 1H NMR (300 MHz, acetone-d6): delta 7.16 (d, J=3.4, 1H), 6.47 (d, J=3.4, 1H), 4.59 (s, 2H) ; 13C NMR (75 MHz, acetone-d6): delta 160.9, 159.5, 144.9, 119.6, 109.6, 57.3. [0061] DHMF: 1H NMR (300 MHz, acetone-d6): delta 6.18 (s, 2H), 4.48 (d, J=5.8, 4H), 4.18 (t, J=5.8, 2H) ; 13C NMR (75 MHz, acetone-d6): delta 155.8, 108.22, 57.2. | |
With 1-butyl-3-methylimidazolium Tetrafluoroborate; sodium hydroxide; at 0 - 20℃; | DHMF and HMFA were prepared in the same manner as in Example 1, with the exception that 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm]BF4, available from C-TRI) was used as the ionic liquid instead of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIm]TFSI). [0075] The melting point of the light yellow crystals was 239.5° C., and the light yellow crystals were analyzed to be the target compound using 1H-NMR, 13C-NMR. The analytic data was as follows. [0076] HMFA: 1H NMR (300 MHz, acetone-d6): delta 7.16 (d, J=3.4, 1H), 6.47 (d, J=3.4, 1H), 4.59 (s, 2H) ; 13C NMR (75 MHz, acetone-d6): delta 160.9, 159.5, 144.9, 119.6, 109.6, 57.3. [0077] DHMF: 1H NMR (300 MHz, acetone-d6): delta 6.18 (s, 2H), 4.48 (d, J=5.8, 4H), 4.18 (t, J=5.8, 2H) ; 13C NMR (75 MHz, acetone-d6): delta 155.8, 108.22, 57.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen; In water; at 90℃; under 6000.6 Torr; for 24h;Autoclave;Catalytic behavior; | General procedure: As a general procedure, the oxidation of HMF was performed under a vigorous stirring in a stainless steel autoclave in the presence of molecular O2 (8 bars), 1 mmole of substrate (HMF), 10 mLsolvent, 0.05 g of catalyst and a temperature of 90C for 24 h. All the changes of reaction parameters: temperature, pressure, solvent, amount of the catalysts or reaction time were notified inthe text. After ending the HMF oxidation and filtering off the catalyst, the mother liquor was diluted 5 times and the products were analyzed by high performance liquid chromatography (HPLC), ona Thermo Scientific Accela 600 device equipped with a UV-vis detector and a Rezex-ROA H+column. 5-Hydroxymethyl furfural(HMF), diformyl furan (DFF), 5-hydroxymethyl-2-furancarboxylicacid (HMFCA), 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA) from Sigma-Aldrich were used as standards. The maximum of absorption for FDCA and HMFCA corresponded to = 260 nm while for HMF, FFCA and DFF to = 285 nm. The mobile phase consisted of 0.05 N H2SO4, at a flow rate of 0.5 mL/min, and the analysis was carried out at 40C, using a two channels detection (260 nm and 285 nm) and an injection volume of 3 L. A carbon mass balance of 98-99% was obtained for all the performed reactions. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide; In water; at 25℃; under 760.051 Torr; for 24h;Green chemistry; | The catalytic activity performance of the metal Salen complexessupported on SBA-15 (Co/SBA-15, Fe/SBA-15 and Cu Salen/SBA-15) inthe oxidation of HMF were evaluated. The HMF oxidation reaction wascarried out in an aqueous system at neutral pH (the pH was not adjusted)using H2O2 as oxidant agent. The reaction was performed undermild conditions (aqueous media, neutral pH, atmospheric temperatureand pressure). The system consisted of a 125 mL round-bottom flaskwith a refrigerant column to avoid the HMF volatilization. All testswere performed with an initial substrate HMF 0.4 mM [8], 50 mL reactionvolume, H2O2 30 w/Vpercent (100 muL) as oxidant agent and using0.05 g of catalyst. Aliquots of 500 muL were taken during 24 h, fromwhich 75 muL were injected in the chromatograph for their analysis. Thesamples were taken in short periods of time at the early minutes of thereaction, and in a longer period as the reaction advanced in order tohave enough information for the kinetic study. The reaction mixturewas stirred at a constant 500 rpm. Tests were done at low temperatures25, 30 and 40 °C to know how the temperature affects the reaction.Although the catalyst can be used at higher moderate temperatures,40 °C level was selected as the maximum temperature to avoid H2O2degradation. Temperature levels were recorded with thermocouplespreviously connected to a temperature monitoring program using theLabview System Design Software. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60.26%; 5.9%; 25.45% | With 10% Pt/activated carbon; oxygen; sodium carbonate; In water; at 100℃; under 7500.75 Torr; | General procedure: Oxidation of HMF to obtain FFCA Reactant HMF (5 mg/mL) in wateEach CatCart (70x4 mm) was filled first with 20 mg Celite 545 and then 280 mg 10% Pt/C were added. Fresh CatCart was used every time, when the system pressure was changed. Before each screening series, the entire reaction line was purged with H20 (HPLC Grade), the Teflon frit of the system valve was replaced and ThalesNano X-Cube System Self-Test was performed. The initial system stabilization was always achieved using H20 (HPLC Grade) and when the reaction parameters remained constant, the pumping of the reaction solution began, then the system was allowed to stabilize and equilibrate at the new conditions for 10 min and two samples of 1 mL each were then collected. Then the temperature was increased and the system was again allowed to stabilize (the same procedure was applied for all temperatures within the experimental series). In all the cases 40 bar difference between the system pressure and the external gas pressure was provided for good system stability. At a temperature of 100C, an ideal compromise between substrate conversion and product selectivity regarding the product FFCA was achieved. r.Base additive Na2C03 (2 equiv. based on HMF, premixed with HMF solution) Catalyst 10% Pt/C (280 mg 10% Pt/C + 20 mg Celite 545) Oxidant synthetic air. Reactor System ThalesNano X-Cube, pump flow rate: 0.5mL/min, residence time: 2 min Table 6 below there is set out a summary of the results from HMF-FFCA oxidation screening in flow using the following parameters: 1 mL HMF (5 mg/mL), 2 equiv. Na2C03, H20, 10% Pt/C, 80 bar Air, 60-160C, 0.5 mL/min, 2 min. Table 6 it is evident that under the given conditions a high FFCA yield and a high FFCA selectivity may be achieved. The yield in average is increasing with increasing temperature up to approx. 120C. A temperature yielding FFCA in a range of approx. 45 to 60% related to the starting material HMF is in the range from 60C to 160C, in particular from 80 to 140C, e.g. 100 to 120C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.65%; 20.15% | With 10% Pt/activated carbon; oxygen; sodium hydroxide; In water; at 120℃; under 60006 Torr; | General procedure: Oxidation of HMF to obtain HMFCA Reactant HMF (5 mg/mL) in water .Catalyst K-OMS-2 (263.4 mg K-OMS-2 + 50 mg Celite 545) prepared according to Angew. Chem. Int. Ed. 2012, 51, 544-547. Oxidant oxygen or synthetic air, Reactor System ThalesNano X-Cube, pump flow rate: 0.5 mL/min, residence time:2/4 min (0108) Each CatCart (70x4 mm) was filled first with 50 mg Celite 545 and then 263.4 mg K-OMS-2 were added. Fresh CatCart was used every time, when the system pressure was changed. Before each screening series, the entire reaction line was purged with H2O (HPLC Grade), the Teflon frit of the system valve was replaced and ThalesNano X-Cube System Self-Test was performed. The initial system stabilization was always achieved using H2O (HPLC Grade) and when the reaction parameters remained constant, the pumping of the reaction solution began, then the system was allowed to stabilize and equilibrate at the new conditions for 10 min and two samples of 1 mL each were then collected. Then the temperature was increased and the system was again allowed to stabilize (the same procedure was applied for all temperatures within the experimental series). In all the cases 40 bar difference between the system pressure and the external gas pressure was provided for good system stability. The experiments were carried out using one or two catalyst cartridges offering ideal reaction conditions to produce DFF in good yield (-70%) requiring only 10 bar of oxygen partial pressure.To reduce the hazardous potential of pure oxygen, the reactions were also performed substituting oxygen with synthetic air. However, to reach similar yields, the pressure had to be increased to 80 bar of compressed air. In Table 2 below there is set out a summary of the results from HMF-DFF oxidation screening in flow using the following parameters:1 mL HMF (5 mg/mL), H20, K-OMS-2/Celite, 10 bar 02, 100-160C, 0.5 mL/min, 2 (using one catalyst cartridge). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9%Spectr.; 72%Spectr.; 19%Spectr. | With boron tribromide; germaniumtetrachloride; at 100℃; for 10h; | 1.8 g of sucrose,0.271 g of GeCl4, 0.091 g of BBr3, and 20 mL of n-propanol were added to 50 mL of a polyTetrafluoroethylene-lined stainless steel reactor,Heated to l00 C,The reaction was carried out at that temperature for 10 h. Filtration,To remove unreacted sucrose and other insoluble impurities,The solvent was removed by rotary evaporation,2 mL H20 was added and the organic phase was extracted with methyl isobutyl ketone,The resulting organic phase was rotary evaporated to a high purity furan derivative,The isolated yield was 83%. The qualitative analysis of the reaction products was carried out by gas chromatography-mass spectrometry (GC-MS)And with the standard material (HMF,5-propoxymethylfurfural and propyl propionate) in gas chromatography (GC) were compared and confirmed. Quantitative analysis of the yield distribution of different furan derivatives was confirmed by 1H NMR,The product distribution results are:5-propoxymethylfurfural was 72%, HMF was 9%Propyl propionate was 19% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; 1,3-bis-(diphenylphosphino)propane; sodium carbonate; In 2-methyltetrahydrofuran; at 125℃; for 24h;Molecular sieve; Inert atmosphere; Sealed tube; | General procedure: Rh(cod)2BF4(6 mol%), DPPP (0.09 mmol), Na2CO3 (1 mmol) and 4A MS (SiO2,powder, 150 mg) were transferred into an oven-dried tube (15 mL), which was evacuated and backfilled with N2 (5x). 2-Methyltetrahydrofuran (2.5 mL), alkyl or aryl iodide (1 mmol),HMF (1.2 mmol) were added into the tube via syringe and sealed with Teflon plug. The reaction mixture was stirred at 125 C for24 h. After the reaction was complete, the mixture was concentrated by rotary evaporation. The crude product was purified by column chromatography (EA/PE = 1/20) on a silica gel to afford the desired product. |
Tags: 67-47-0 synthesis path| 67-47-0 SDS| 67-47-0 COA| 67-47-0 purity| 67-47-0 application| 67-47-0 NMR| 67-47-0 COA| 67-47-0 structure
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P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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