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Product Details of [ 10551-58-3 ]

CAS No. :10551-58-3 MDL No. :MFCD00003233
Formula : C8H8O4 Boiling Point : -
Linear Structure Formula :- InChI Key :QAVITTVTXPZTSE-UHFFFAOYSA-N
M.W : 168.15 Pubchem ID :66349
Synonyms :

Calculated chemistry of [ 10551-58-3 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 12
Num. arom. heavy atoms : 5
Fraction Csp3 : 0.25
Num. rotatable bonds : 4
Num. H-bond acceptors : 4.0
Num. H-bond donors : 0.0
Molar Refractivity : 39.96
TPSA : 56.51 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.96 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.61
Log Po/w (XLOGP3) : 0.51
Log Po/w (WLOGP) : 1.0
Log Po/w (MLOGP) : -0.5
Log Po/w (SILICOS-IT) : 1.6
Consensus Log Po/w : 0.84

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -1.25
Solubility : 9.5 mg/ml ; 0.0565 mol/l
Class : Very soluble
Log S (Ali) : -1.27
Solubility : 9.09 mg/ml ; 0.0541 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -2.03
Solubility : 1.55 mg/ml ; 0.00925 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 2.48

Safety of [ 10551-58-3 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P305+P351+P338 UN#:N/A
Hazard Statements:H319 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 10551-58-3 ]

* 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.

  • Downstream synthetic route of [ 10551-58-3 ]

[ 10551-58-3 ] Synthesis Path-Downstream   1~100

  • 1
  • [ 67-47-0 ]
  • [ 108-24-7 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
95% With pyridine In dichloromethane at 20℃; for 18h; Inert atmosphere; 5-Acetoxymethyl-2-furaldehyde (1p) To the mixture of 5-(hydroxymethyl)furfural (HMF, 3.5 g, 27.8 mmol) and acetic anhydride (4.3 mL, 45.6 mmol) in anhydrous DCM (30 mL) pyridine (0.5 mL, 6.2 mmol) was added stirred at room temperature for 18 hours under argon atmosphere. The solvents were evaporated under reduced pressure and the crude residue was purified by column chromatography on silica gel (ethyl acetate/hexane) affording product 1p as a colorless oil with 95% yield (4.4 g); 1H NMR (200MHz, CDCl3) δ 9.62 (s, 1H), 7.24-7.12 (m, 1H), 6.57 (d, J = 3.5 Hz, 1H), 5.10 (s, 2H), 2.09 (s, 3H); 13C NMR (50 MHz, CDCl3) δ178.02, 170.81, 155.64, 153.44, 121.91, 112.79, 58.01, 20.89. 1H and 13C NMR data were in accordance with those reported in the literature.[J. A. S. Coelho, A. F. Trindade, V. Andr, M. T. Duarte, L. F. Veiros, C. A. M. Afonso, Org. Biomol. Chem. 2014,12,9324-9328]
93% With pyridine In acetonitrile at 20℃; for 22h; Inert atmosphere;
90% With dmap In ethyl acetate 1.i Example-1:
Preparation of 2,5-furandicarboxylic acid (FDCA):
(i) Preparation of 5-acetyIoxymethylfurfural (4): [R=CH3] Example-1:Preparation of 2,5-furandicarboxylic acid (FDCA):(i) Preparation of 5-acetyIoxymethylfurfural (4): [R=CH3]Into a 250 mL four necked round bottomed flask equipped with a mechanical stirrer, a reflux condenser and a thermometer socket are charged 5-hydroxymethylfurfural (25 g; 0.198 mol), ethyl acetate (125 mL) and DMAP (2.42 g; 0.019). To the cooled solution, acetic anhydride (24.3 g; 0.238 mol) was added. After addition, the reaction mixture was stirred for 1 -2 hours. The reaction mixture was then washed with water and the resulting layers were separated. The organic layer was distilled off under diminished pressure to get 5-acetoxymethylfurfural (30.0 g; 90% by theory) as yellow oil. HPLC: > 98%
89% With pyridine In acetonitrile at 20℃; for 3h; Inert atmosphere; 11 preparation of 5-[(acetoxy)methyl]furfural This example describes the conversion of HMF to AMF with acetic anhydride, and base. In a 50-mL Schlenk flask, pyridine (0.032 mL, 0.4 mmol) was added to a solution of HMF (0.25 g, 2 mmol) and acetic anhydride (0.28 mL, 3 mmol) in 10 mL of MeCN under argon atmosphere. The resulting orange solution was stirred at RT for 3 h. Solvent and volatile compounds were removed under vacuum to yield AMF as an orange oil. Yield: 0.30 g (89%).
89% With sodium acetate; acetic acid for 5.5h; Reflux;
87% With pyridine In acetonitrile at 20℃; Inert atmosphere; Darkness;
81% With sodium acetate at 80℃; for 2.5h;
62% With pyridine In acetonitrile at 0 - 20℃; for 15.5h;
62% With pyridine In acetonitrile at 0 - 20℃; for 15.5h; 1.I (5-formyIfuran-2-yl)methyl acetate (VZHE004) 5-HMF (63 mg, 0.5 mmol) and acetic anhydride (102 mg, 1 mmol) were dissolved in 2 mL of ACN, and the mixture was cooled to 0 °C. Pyridine (79 mg, 1 mmol) was added slowly. The resultant reaction mixture was stirred at 0 °C for 30 min and then at rt for 15 h. The reaction mixture was diluted with EtOAc (15 mL), and then washed with 0.1 N HC1 (5 mL x 3), 10% NaHC03 (5 mL x 2), and brine (5 mL). The organic layer was then dried with Na2S04. After filtration and concentration, the resultant crude oil was purified with column, and eluted with the solvent system of EtOAc : hexanes = 1 :4 to give 52 mg of the product as a colorless oil, and the yield was 62%.1H-NMR (CDC13): δ 9.64 (s, 1H), 7.20 (d, J= 3.52 Hz, 1H), 6.58 (d, J= 3.56 Hz, 1H), 5.12 (s, 2H), 2.1 1 (s, 3H). 13C-NMR (CDC13): δ 177.92, 170.41, 155.61, 153.08, 121.58, 112.66, 57.96, 20.80.
39% With pyridine In acetonitrile at 20℃; for 16h; Cooling with ice; Inert atmosphere;
With sodium acetate
With pyridine In acetonitrile at 20℃; for 3h; Inert atmosphere;
With pyridine at 20℃; for 16h;
With triethylamine In acetonitrile at 20℃; for 1h; 7 Synthesis of HMF acetate form To an acetonitrile solution (0.1 mol / L) in which HMF (manufactured by Sigma-Aldrich) was dissolved, 1.5 molar equivalents of acetic anhydride and 2 molar equivalents of triethylamine were added. The hydroxyl group of HMF was converted to acetate by stirring at room temperature for 1 hour. The obtained product was purified by column chromatography to obtain an HMF acetate.
With triethylamine In acetonitrile at 20℃; for 1h; 7 Synthesis of HMF Acetate Body 1.5 molar equivalent of acetic anhydride and 2 molar equivalent of triethylamine were added to an acetonitrile solution (0.1 mol / L) in which HMF (manufactured by Sigma-Aldrich) was dissolved and stirred at room temperature for 1 hour The hydroxyl group of HMF was converted to acetate. The obtained product was purified by column chromatography to obtain an HMF acetate.
With dmap at 20℃; 1.2 2) Acetylation of HMF 4-(Dimethylamino)pyridine (DMAP, 0.68 g, 5.55 mmol) and acetic anhydride (Ac2O, 6.3 mL, 66.6 mmol) were added to the reaction solution and stirred at room temperature, and the reaction progress was confirmed by TLC.When the reaction is complete, the reactant is dissolved with ethyl acetate, washed several times with water, and the organic layer is separated.The organic layer is dried over Na2SO4, filtered, and the filtrate is vacuum distilled to obtain the desired compound, 5-Acetoxymethyl-2-furfural (AMF).TLC confirmation: n-Hexane: Ethyl acetate = 1:2 Rf = 0.8, average yield 80%

Reference: [1]Koszelewski, Dominik; Ostaszewski, Ryszard [Bioorganic Chemistry, 2019, vol. 93]
[2]Coelho, Jaime A. S.; Trindade, Alexandre F.; Andr, Vnia; Teresa Duarte; Veiros, Luis F.; Afonso, Carlos A.M. [Organic and Biomolecular Chemistry, 2014, vol. 12, # 46, p. 9324 - 9328]
[3]Current Patent Assignee: NATCO PHARMA LIMITED - WO2015/56270, 2015, A1 Location in patent: Page/Page column 9
[4]Current Patent Assignee: UNIVERSITY OF ILLINOIS (SYSTEM) - US2011/263880, 2011, A1 Location in patent: Page/Page column 13
[5]Phutdhawong, Weerachai; Inpang, Siwaporn; Taechowisan, Thongchai; Phutdhawong, Waya S. [Oriental Journal of Chemistry, 2019, vol. 35, # 3, p. 1080 - 1085]
[6]Pezzetta, Cristofer; Veiros, Luis F.; Oble, Julie; Poli, Giovanni [Chemistry - A European Journal, 2017, vol. 23, # 35, p. 8385 - 8389]
[7]Cottier; Descotes; Eymard; Rapp [Synthesis, 1995, # 3, p. 303 - 306]
[8]Xu, Guoyan G.; Pagare, Piyusha P.; Ghatge, Mohini S.; Safo, Ronni P.; Gazi, Aheema; Chen, Qiukan; David, Tanya; Alabbas, Alhumaidi B.; Musayev, Faik N.; Venitz, Jürgen; Zhang, Yan; Safo, Martin K.; Abdulmalik, Osheiza [Molecular Pharmaceutics, 2017, vol. 14, # 10, p. 3499 - 3511]
[9]Current Patent Assignee: VIRGINIA COMMONWEALTH UNIVERSITY; THE CHILDREN'S HOSPITAL OF PHILADELPHIA - WO2018/18035, 2018, A1 Location in patent: Page/Page column 33
[10]Banz Chung, Elise M.-J.; Da Cunha, Igor Tadeu; Magee, Megan; Moore, Cameron M.; Schlaf, Marcel; Soltanipanah, Parnian; Stones, Maryanne K.; Sullivan, Ryan J.; Sutton, Andrew D.; Umphrey, Gary J. [ACS Catalysis, 2020, vol. 10, # 4, p. 2667 - 2683]
[11]Karashima [Hoppe-Seyler's Zeitschrift fur Physiologische Chemie, 1929, vol. 180, p. 242]
[12]Thananatthanachon, Todsapon; Rauchfuss, Thomas B. [Angewandte Chemie - International Edition, 2010, vol. 49, # 37, p. 6616 - 6618]
[13]Walia, Mayanka; Sharma, Upendra; Agnihotri, Vijai K.; Singh, Bikram [RSC Advances, 2014, vol. 4, # 28, p. 14414 - 14418]
[14]Current Patent Assignee: Mitsubishi Chemical Corp (in: MCHC Group); HOKKAIDO UNIVERSITY; MITSUBISHI CHEMICAL HOLDINGS CORPORATION - JP2018/39778, 2018, A Location in patent: Paragraph 0132
[15]Current Patent Assignee: HOKKAIDO UNIVERSITY; MITSUBISHI CHEMICAL HOLDINGS CORPORATION; Mitsubishi Chemical Corp (in: MCHC Group) - JP2018/39779, 2018, A Location in patent: Paragraph 0136
[16]Current Patent Assignee: UNI PLUS - KR2021/72855, 2021, A Location in patent: Paragraph 0090; 0094-0097
  • 2
  • [ 61-54-1 ]
  • [ 10551-58-3 ]
  • [ 115107-77-2 ]
YieldReaction ConditionsOperation in experiment
56% With trifluoroacetic acid In dichloromethane at 20℃; for 48h; Molecular sieve;
Stage #1: tryptamine; 5-acetoxymethyl-2-furaldehyde With toluene-4-sulfonic acid In benzene Reflux; Inert atmosphere; Stage #2: With hydrogenchloride In tetrahydrofuran at 20℃; Inert atmosphere;
  • 3
  • [ 10551-58-3 ]
  • [ 107-21-1 ]
  • [ 126380-42-5 ]
YieldReaction ConditionsOperation in experiment
84% With toluene-4-sulfonic acid In benzene for 6h; Heating;
With indium(III) triflate; trimethyl orthoformate In dichloromethane at 20℃; 7 Synthesis of EG-HMF The HMF acetate obtained by the above method was dissolved in dichloromethane solution (HMF acetate concentration: 0.1 mol / L)a catalytic amount (0.01 equivalent) of indium trifluoromethanesulfonate (In(OTf)3)and an excess amount of trimethyl orthoformate and ethylene glycol were added,the aldehyde moiety bound to the furan ring was converted to a cyclic acetal by stirring at room temperature. Finally, the product was reacted with sodium carbonate in a methanol solution to decompose the acetate site to obtain the objective ethylene glycol-HMF acetal (EG-HMF).
With indium(III) triflate; trimethyl orthoformate In dichloromethane at 20℃; for 15h;
  • 4
  • [ 10551-58-3 ]
  • [ 67-47-0 ]
YieldReaction ConditionsOperation in experiment
98% With potassium carbonate In methanol for 12h;
98% With potassium carbonate In methanol at 20℃; for 18h;
92% With bis(tri-n-butyltin)oxide In benzene at 80℃; for 8h;
92% With bis(tri-n-butyltin)oxide In benzene at 80℃; for 8h;
92% With bis(tri-n-butyltin)oxide In benzene at 80℃; for 8h;
67% With methanol at 25 - 30℃; for 1h; 2B Example 2B; Hydrolysis of 5-acetoxymethylfurfural Using a Basic Ion Exchanger; 10.9 kg (65 mol) of 5-acetoxymethylfurfural were dissolved in 60 1 of methanol and admixed with stirring with 1.1 kg of dried strongly basic Amberlyst A26 OH ion exchanger (styrene-divinylbenzene copolymer resin with quaternary ammonium groups (type 1) in OH form, obtainable from Rohm and Haas Company, Philadelphia, U.S.A.) at 25-30° C. After 1 h, the reaction mixture was admixed with 1 kg of activated carbon, stirred for 60 min, filtered through Celite and washed with 10 1 of methanol. The clear methanolic solution was concentrated at not more than 40° C. under reduced pressure. The residue was admixed with 8 l of MtBE and cooled slowly to 5° C. The precipitated product was filtered off with suction, washed with 1.5 l of ice-cold MtBE and dried at 20° C. under reduced pressure.Yield: 7.01 kg (56 mol, 86% based on 5-acetoxymethylfurfural, 36% based on D-fructose) of 5-hydroxymethylfurfural. Alternatively, the residue can be distilled in a short-path evaporator at 90° C./0.03 mbar (yield: 5.42 kg (43 mol, 67% based on 5-acetoxymethylfurfural, 28% based on D-fructose)).The purity of the 5-hydroxymethylfurfural prepared was >99% in all examples, as determined with the aid of HPLC and NMR.
63% With methanol; potassium carbonate at 20 - 25℃; for 1h; 1B Example 1B; Hydrolysis of 5-acetoxymethylfurfural Using Potassium Carbonate; 179.1 g (1.07 mol) of the 5-acetoxymethylfurfural prepared in Example 1A were dissolved in 1.1 1 of methanol and admixed at 20-25° C. with 140 g (1.01 mol) of potassium carbonate with stirring. After 1 h, the reaction mixture was admixed with 10 g of activated carbon and stirred for 20 min, and the solid constituents were filtered off and washed with 100 ml of MeOH. The clear methanolic solution was concentrated under reduced pressure on a rotary evaporator. The residue was admixed with 300 ml of MtBE. The precipitated salts were filtered off and washed with 20 ml of MtBE. The solution was concentrated on a rotary evaporator and the residue was distilled in a short-path evaporator at 90° C./0.03 mbar. Yield: 85.2 g (0.68 mol, 63% based on 5-acetoxymethylfurfural, 29% based on D-fructose). Alternatively, the residue can also be admixed with MtBE, and the product crystallized at 0° C. (yield: 98.4 g) (0.78 mol, 73% based on 5-acetoxymethylfurfural, 33% based on D-fructose)).
With methanol at 20 - 60℃; for 0.166667h; 3 Example 3Preparation of HMF from Fructose Using a HMF Ester Intermediate; This example illustrates the use of the present methods to deprotect HMF ester to provide substantially pure HMF. The feed material was prepared and placed in a vial of methanol and Amberlyst A26OH resin obtained from Rohm and Haas Company (Woodridge, Ill.). Amberlyst A26OH resin is a strong base, type 1, anionic, macroreticular polymeric resin based on crosslinked styrene divinylbenzene copolymer containing quaternary ammonium groups. After sitting at room temperature for about 5 minutes, the material was analyzed by thin layer chromatography (tlc) to show deacylation. The solid yield was about 85% HMF with about 8% AcHMF determined by a Shimadzu QP-2010 GC Mass spectrometer. The chromatogram is shown in FIG. 5. The remaining material was residual methanol. Heating the methanol solution with a heat gun to 60° C. for less than 5 minutes converted the remaining AcHMF to HMF. Alternatively, passing the product through the chromatography column with a solid phase catalyst would convert the remaining AcHMF to HMF.
Multi-step reaction with 3 steps 1: trimethyl orthoformate; indium(III) triflate / dichloromethane / 15 h / 20 °C 2: sodium carbonate; water / ethanol / 5 h / 20 °C 3: sodium carbonate / 139.84 °C / 750.08 Torr / Autoclave

  • 5
  • [ 10551-58-3 ]
  • [ 120047-86-1 ]
YieldReaction ConditionsOperation in experiment
90% With Sephadex resin; oxygen; rose bengal In ethanol at 20℃; Irradiation;
81% With oxygen; Rose Bengal lactone In water; isopropyl alcohol at 0℃; Inert atmosphere; Darkness; Flow reactor; Green chemistry;
  • 6
  • [ 67-47-0 ]
  • [ 64-19-7 ]
  • [ 823-82-5 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
57% With zirconium tetraacetate; acetaldehyde; sodium bromide at 75℃; for 5.16667h;
With air In butanone at 115 - 125℃; for 6h; 10 SYNTHESIS OF DFF FROM HMF USING AIR Example 10 [0046] A reaction mixture containing 97% purity HMF (5.00 g), acetic acid (50 mL), cobalt acetate (0.97 g), manganese acetate (0.97 g), and methyl ethyl ketone (0.89 mL) was placed in a 100 mL reactor and subjected to 1000 psi air at 115C for 4 hours. A sample taken at 4 hours was subjected to TLC analysis as described in example 1. Visual analysis indicated partial conversion of HMF to DFF and the AcHMF ether. The temperature was then increased to 125C for an additional 2 hours. The catalysts were removed by filtration and the solvent evaporated. The product was washed with water to give a cream colored solid. H NMR analysis of the isolated solid indicated a 1:1 mixture of DFF and 5-acetoxymethylfurfural with essentially complete conversion of HMF.. NMR (δ, IH): 10.2 (s, 2.0 H) DFF; 7.82 (s, 2.0 H) DFF; 9.84 (s, 1.0H) AcHMF; 7.86 (d, IH) AcHMF; 6.98 (d, IH) AcHMF; 5.42 (s, 2H) AcHMF; 2.42 (s, 3H) AcHMF.
  • 7
  • [ 108-24-7 ]
  • [ 66-84-2 ]
  • [ 10551-58-3 ]
  • Acetic acid 2,3,4-triacetoxy-1-[5-((E)-3,4-diacetoxy-but-1-enyl)-pyrazin-2-yl]-butyl ester [ No CAS ]
  • acetic acid 2,3-diacetoxy-1-{acetoxy-[5-(2,3,4-triacetoxy-butyl)-pyrazin-2-yl]-methyl}-propyl ester [ No CAS ]
  • 8
  • [ 10551-58-3 ]
  • [ 120040-08-6 ]
YieldReaction ConditionsOperation in experiment
80% Stage #1: 5-acetoxymethyl-2-furaldehyde With sodium tetrahydroborate In ethanol at 0℃; for 0.166667h; Stage #2: With bromine In methanol; water
Multi-step reaction with 2 steps 1: NaBH4 / ethanol / 0.17 h / 0 °C 2: 894 mg / bromine / H2O; methanol / 2 h
  • 9
  • [ 10551-58-3 ]
  • [ 89630-82-0 ]
YieldReaction ConditionsOperation in experiment
With sodium tetrahydroborate In ethanol at 0℃; for 0.166667h;
With hydrogen In ethanol at 190℃; for 1h; 18 Pure acetoxymethylfurfural (AcHMF, 5 g) was placed in a 100 mL reactor vessel with G-22/2 barium promoted copper chromite catalyst (0.5 g) and ethanol (70 mL). Hydrogenation was performed at 1900C and 950 psi for 1 hour. GC/MS revealed partial hydrogenation of AcHMF.
With sodium tetrahydroborate In methanol at 0 - 20℃; Inert atmosphere;
Multi-step reaction with 2 steps 1: [RhCl2(p-cymene)]2 / toluene / 4 h / 20 °C / Inert atmosphere; Glovebox 2: water; silica gel / toluene / 3 h / 50 °C
82 %Chromat. With hydrogen In methanol at 150℃; for 12h; Autoclave;

  • 10
  • [ 10551-58-3 ]
  • [ 1136-86-3 ]
  • C17H18O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% With sodium hydroxide In methanol 2 Preparation of Chalcone 2 was accomplished by Claisen-Schmidt condensation, as follows. In 5 mL methanol were dissolved 1.43 g (6.8 mmol) of 3,4,5-trimethoxyacetophenone and 1.14 g (6.8 mmol) of 5-acetoxymethyl-2-furaldehyde. After addition of 0.37 g crushed NaOH, the reaction mixture was stirred overnight to yield a dark solid material. This was taken up in methanol, collected by filtration, and washed with ice water to yield a mustard yellow powder (1.35 g, 55%). The material was recrystallized from H2O-methanol. Mp 86-88° C. 1H NMR (CDCl3) δ (ppm) 2.2 (br s, 1H), 3.93 (s, 3H), 3.95 (s, 6H), 4.70 (s, 2H), 6.42 (d, J=3.3 Hz, 1H), 6.67 (d, J=3.3 Hz, 1H), 7.28 (s, 2H), 7.38 (d, J=15.3 Hz, 1H), 7.56 (d, J=15.6 Hz, 1H).
  • 12
  • [ 10551-58-3 ]
  • [ 1779-49-3 ]
  • [ 59288-25-4 ]
YieldReaction ConditionsOperation in experiment
68% Stage #1: Methyltriphenylphosphonium bromide With sodium hydride In diethyl ether at 0℃; for 1h; Stage #2: 5-acetoxymethyl-2-furaldehyde In diethyl ether for 24h; Further stages.;
  • 13
  • [ 10551-58-3 ]
  • [ 29700-20-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: p-toluenesulfonic acid / benzene / 3 h / Heating 2: HCl / 1,2-dimethoxy-ethane; diethyl ether / 2 h / Ambient temperature 3: 50 percent / oxygen / 5percent Pt/C / toluene / 8 h / Heating 4: 70 percent / conc. aq. NH4OH / methanol / 3 h / Ambient temperature
Multi-step reaction with 2 steps 1: (i) AcOH, (ii) aq. K2Cr2O7, H2SO4 2: aq. NH3 / methanol
Multi-step reaction with 3 steps 1.1: toluene-4-sulfonic acid / benzene / Reflux; Inert atmosphere 1.2: 20 °C / Inert atmosphere 2.1: palladium on activated charcoal / toluene / Reflux; Inert atmosphere 3.1: ammonia / methanol / 20 °C / Inert atmosphere
Multi-step reaction with 3 steps 1: trifluoroacetic acid / dichloromethane / 48 h / 20 °C / Molecular sieve 2: trichloroisocyanuric acid; triethylamine / N,N-dimethyl-formamide / 2 h / 20 °C 3: sodium methylate / dichloromethane; methanol / 3 h / 20 °C

  • 15
  • [ 1623-88-7 ]
  • [ 64-19-7 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
50% With potassium carbonate In acetonitrile at 20℃; for 5h; 1.2 Potassium carbonate (1 mmol) was added to a mixture of 143 mg (1 mmol) of 5-chloromethylfurancarboxyaldehyde, an alcoholic compound (1-2 mmol) and acetonitrile (10 ml), and the reaction mixture was stirred for 5 hrs at room temperature. After checking completion of the reaction by thin layer chromatography, the solvent was removed from the reaction solution using a vacuum evaporator. Then, ethylacetate (30 ml) and water (30 ml) were added to the residue. The separated organic layer was dried and filtered, and subjected to column chromatography, thus giving oxymethylfuran-2-carboxyaldehyde having a substitution group, with a yield of 50-70%.
With potassium carbonate In acetonitrile at 20℃; for 5h; 1.2 (2) Preparation of oxymethylfuran-2-carboxyaldehyde having a substitution group (Compounds 2 to 30) Potassium carbonate (1 mmol) was added to a mixture of 143 mg (1 mmol) of 5-chloromethylfurancarboxyaldehyde, an alcoholic compound (1-2 mmol) and acetonitrile (10 ML), and the reaction mixture was stirred for 5 hrs at room temperature. After checking completion of the reaction by thin layer chromatography, the solvent was removed from the reaction solution using a vacuum evaporator. Then, ethylacetate (30 ml) and water (30 ml) were added to the residue. The separated organic layer was dried and filtered, and subjected to column chromatography, thus giving oxymethylfuran-2-carboxyaldehyde having a substitution group, with a yield of 50-70%.
Stage #1: acetic acid With potassium carbonate In N,N-dimethyl-formamide for 0.5h; Stage #2: 5-chloromethylfurfural In N,N-dimethyl-formamide at 20℃;
  • 16
  • [ 67-47-0 ]
  • [ 10049-21-5 ]
  • [ 75-36-5 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
With pyridine In dichloromethane 7 STAGE A: 5-(acetyloxy) methyl-2-furancarboxaldehyde STAGE A: 5-(acetyloxy) methyl-2-furancarboxaldehyde 10.05 cm3 of acetyl chloride is added at 5° C. to a solution containing 16.2 g of 5-(hydroxy methyl) 2-furan-carboxaldehyde and 200 cm3 of methylene chloride. Then 11.4 cm3 of pyridine and 50 cm3 of methylene chloride are added. The reaction mixture is maintained under agitation for 3 hours at 20° C. It is then treated with an aqueous solution of sodium acid phosphate and extracted with methylene chloride, followed by drying and concentrating. After chromatography on silica eluding with a hexane--ethyl acetate mixture (7-3), 19.35 g of desired product is obtained.
  • 17
  • [ 10551-58-3 ]
  • [ 88579-22-0 ]
  • (E)-1-(5-Acetoxymethyl-2-furanyl)-2-(3,4-dihydro-4,4-dimethyl-2H-1-benzopyran-6-yl)propene [ No CAS ]
YieldReaction ConditionsOperation in experiment
0.12 grams (19%) With n-butyllithium In hexane; ethyl acetate (E)-1-(5-Acetoxymethyl-2-furanyl)-2-(3,4-dihydro-4,4-dimethyl-2H-1-benzopyran-6-yl)propene (52) (E)-1-(5-Acetoxymethyl-2-furanyl)-2-(3,4-dihydro-4,4-dimethyl-2H-1-benzopyran-6-yl)propene (52) A solution of n-butyllithium in hexane (1.55M, 1.23 mL, 1.88 mmol) was added dropwise under N2 to a stirred suspension of the precursor phosphonium salt 51 (1 g, 1.88 mmol) in dry ether (20 mL). The resulting solution was cooled to -78° C., and a solution of 5-acetoxymethyl-2-furanaldehyde (0.316 g, 1.88 mmol) was added over a period of 1 minute. The solution was stirred for a few minutes at -78° C. and then at room temperature for 24 hours. The mixture changed from reddish-brown to a pale brown color. After 24 hours, the reaction mixture was filtered. The resulting solid was washed with 45 mL of ether (anhydrous), and the filtrate was concentrated to give a yellow oil. This yellow oil was refrigerated for 24 hours and became a dark yellow solid. This solid was passed through 20 grams of silica gel [column, (8*200 MM)]. The product was eluted with 300 mL of hexane:ethyl acetate (4:1) concentration of eluent gave a viscous oil from which yellow solid was obtained after keeping it in ice bath at 0° C. for 5 hours. Recrystallization (hexane) gave 0.12 grams (19%) of the ester (52) as a white crystaline solid: mp 80°-81° C. 1 H NMR (DCCl3) δ1.37 [s, 6H, H(9), H(10)], 1.85 [m, 2H, H(3)], 2.1 [s, 3H, H(20)], 2.36 [s, 3H, H(12)], 4.20 [m, 2H, H(2)], 5.08 [s, 2H, H(18)], 6.31 [d, 1H, J=3 Hz H(16)], 6.46 [d, 1H, J=3 Hz H(5)], 6.53 [s, 1H, H(13)], 6.77 [d, 1H, J=9 Hz, J=3 Hz H(8)], 7.21 [dd, 1H, H(7)], 7.39 [d, 1H, H(15)]; 13 C NMR (DCCl3) ppm 18.24 [C(12)], 20.94 [C(20)], 30.69 [C(4)], 31.06 [C(9), C(10)], 37.63 [C(3)], 58.31 [C(18)], 63.11 [C(2)], 109.54 [C(16)], 114.15 [C(15)], 116.8 [C(8)], 124.36 [C(5)], 124.77 [C(7)], 70.69 [C(19)], non-protonated and vinylic carbons [131.3, 135.6, 136.9, 147.7, 153.3, 154.6]. Mass spectral data for C21 H24 O4: m/e (M=) 340.1674. Found: 340.1679. Anal. calcd. for C 21 H24 O4: C, 74.08; H, 7.06. Found: C, 73.88; H, 7.09. STR31
0.12 grams (19%) With n-butyllithium In hexane; ethyl acetate (E)-1-(5-Acetoxymethyl-2-furanyl)-2-(3,4-dihydro-4,4-dimethyl-2H-1-benzopyran-6-yl)propene (52) (E)-1-(5-Acetoxymethyl-2-furanyl)-2-(3,4-dihydro-4,4-dimethyl-2H-1-benzopyran-6-yl)propene (52) A solution of n-butyllithium in hexane (1.55M, 1.23 mL, 1.88 mmol) was added dropwise under N2 to a stirred suspension of the precursor phosphonium salt 51 (1 g, 1.88 mmol) in dry ether (20 mL). The resulting solution was cooled to -78° C., and a solution of 5-acetoxymethyl-2-furanaldehyde (0.316 g, 1.88 mmol) was added over a period of 1 minute. The solution was stirred for a few minutes at -78° C. and then at room temperature for 24 hours. The mixture changed from reddish-brown to a pale brown color. After 24 hours, the reaction mixture was filtered. The resulting solid was washed with 45 mL of ether (anhydrous), and the filtrate was concentrated to give a yellow oil. This yellow oil was refrigerated for 24 hours and became a dark yellow solid. This solid was passed through 20 grams of silica gel [column, (8*200 MM)]. The product was eluted with 300 mL of hexane:ethyl acetate (4:1) concentration of eluent gave a viscous oil from which yellow solid was obtained after keeping it in ice bath at 0° C. for 5 hours. Recrystallization (hexane) gave 0.12 grams (19%) of the ester (52) as a white crystaline solid: mp 80°-81° C. 1 H NMR (DCCl3) δ1.37 [s, 6 H, H(9), H(10)], 1.85 [m, 2 H, H(3)], 2.1 [s, 3 H, H(20)], 2.36 [s, 3 H, H(12)], 4.20 [m, 2 H, H(2)], 5.08 [s, 2 H, H(18)], 6.31 [d, 1 H, J=3 Hz H(16)], 6.46 [d, 1 H, J=3 Hz H(5)], 6.53 [s, 1 H, H(13)], 6.77 [d, 1 H, J=9 Hz, J=3 Hz H(8)], 7.21 [dd, 1 H, H(7)], 7.39 [d, 1 H, H(15)]; 13 C NMR (DCCl3) ppm 18.24 [C(12)], 20.94 [C(20)], 30.69 [C(4)], 31.06 [C(9), C(10)], 37.63 [C(3)], 58.31 [C(18)], 63.11 [C(2)], 109.54 [C(16)], 114.15 [C(15)], 116.8 [C(8)], 124.36 [C(5)], 124.77 [C(7)], 70.69 [C(19)], non-protonated and vinylic carbons [131.3, 135.6, 136.9, 147.7, 153.3, 154.6]. Mass spectral data for C21 H24 O4: m/e (M-) 340.1674. Found: 340.1679. Anal. calcd. for C21 H24 O4: C, 74.08; H, 7.06. Found: C, 73.88; H, 7.09. STR31
  • 18
  • [ 10551-58-3 ]
  • [ 109-77-3 ]
  • [ 107-95-9 ]
  • [ 120549-80-6 ]
YieldReaction ConditionsOperation in experiment
With acetic acid In dichloromethane; acetonitrile 1 2-(2',2'-dicyanovinyl)-5-acetoxymethyl-furan EXAMPLE 1 2-(2',2'-dicyanovinyl)-5-acetoxymethyl-furan 1,68 g (10 mmol) 5-acetoxymethylfurfuraldehyde and 0,66 g (10 mmol) malononitrile are dissolved in 50 ml acetonitrile and with 40 mg β-alanine and 10 drops acetic acid are boiled at reflux for 10 h. When cooling the solution, the catalyst precipitates and is filtered off. After concentration one get 2,2 g of lilac-coloured crystals with a melting point of 79° C. Recrystalization from methylene chloride yields colourless crystals with m. p.=80°-82° C. IR (KBr): 3130, 3100, 3040, 2990, 2940, 2230, 1750, 1610, 1565, 1225, 1195, 1005, 830 cm-1
  • 19
  • nonahydrated sodium sulfide [ No CAS ]
  • [ 10551-58-3 ]
  • [ 2797-51-5 ]
  • 4,9-dihydro-4,9-dioxo-2-(5-hydroxymethylfuran-2-yl)naphtho[2,3-d]thiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
17% With acetic acid In water 36 4,9-Dihydro-4,9-dioxo-2-(5-hydroxymethylfuran-2-yl)naphtho[2,3-d]thiazole EXAMPLE 36 4,9-Dihydro-4,9-dioxo-2-(5-hydroxymethylfuran-2-yl)naphtho[2,3-d]thiazole 17.36 g (72.2 mmol, 5 eq) of nonahydrated sodium sulfide are dissolved in 70 mL of water. The solution is heated at 60° C., then 3.00 g (14.4 mmol, 1 eq) of 2-amino-3-chloro-1,4-dihydro-1,4-dioxo-naphthalene are added. After 30 min of stirring at 60° C., the solution is cooled to ambient temperature. To the reaction medium, which has turned blue, 2.43 g (14.5 mmol, 1 eq) of 5-acetoxymethyl-2-furaldehyde are added; after 5 min, 3 mL of acetic acid are then added dropwise. The medium turns chestnut brown-orangish; the precipitate formed is filtered through fritted glass, washed with water, and dried to produce 3.30 g of raw product which are purified on a flash column (support: silica 6-35 μm; 5 cm φ, 15 cm h, eluant: CH2Cl2/MeOH, 96/4). The orange product obtained is recrystallized in dimethylformamide, uncolored on animal black, and filtered through Celite and micropores to produce 0.80 g of 4,9-dihydro-4,9-dioxo-2-(5-hydroxymethylfuran-2-yl)naphtho[2,3-d]thiazole in the form of ocher crystals. Yield: 17%; Melting point: >260° C.; Rf: 0.60 (CH2Cl2/MeOH, 96/4); MS (I.E): m/z 311 (M+); 1H-NMR (DMSO-d6): δ (ppm); 8.20 (m, 1H, H-5 or H-8); 8.11 (m, 1H, H-5 or H-8); 7.91 (m, 2H, H-6, H-7); 7.46 (d, 1H, H-3', JH3'-H4'=3.1 Hz); 6.65 (d, 1H, H-4', JH3'-H4'=3.1 Hz); 5.55 (t, 1H, OH, JOH-CH2=5.6 Hz); 4.54 (d, 2H, CH2, JCH2-OH=5.6 Hz); 13C-NMR (DMSO-d6): δ (ppm); 177.6, 176.6 (2C, C-4, C-9); 160.0 (1C, C-5'); 158.4 (1C, C-2); 146.6 (1C, C-2'); 134.4 (2C, C-6, C-7); 132.3, 132.1 (2C, C-4a, C-8a); 127.0, 126.2 (2C, C-5, C-8); 127.0, 126.2 (2C, C-5, C-8); 114.9 (1C, C-3'); 110.5 (1C, C-4'); 55.6 (1C, CH2); IR (Kbr): ν (cm-1); 3374 (OH), 1677 and 1656 (C=O).
  • 20
  • [ 10551-58-3 ]
  • [ 76148-76-0 ]
  • 2-(5-acetoxymethylfuran-2-yl)-4,9-dihydro-4,9-dioxo-naphtho[2,3-d]thiazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
38% With 1-methyl-pyrrolidin-2-one In water; ethyl acetate 37 2-(5-Acetoxymethylfuran-2-yl)-4,9-dihydro-4,9-dioxonaphtho[2,3-d]thiazole EXAMPLE 37 2-(5-Acetoxymethylfuran-2-yl)-4,9-dihydro-4,9-dioxonaphtho[2,3-d]thiazole To 5.00 g (24 mmol) of 2-amino-3-mercapto-1,4-dihydro-1,4-dioxonaphthalene, 40 mL of N-methylpyrrolidone are added at 0° C. under an argon atmosphere. The reaction mixture is stirred for 10 min, then 4.10 g (24 mmol) of 5-acetoxymethyl-2-furaldehyde are added at 0° C. After 5 h of stirring at this temperature, the mixture is allowed to return to ambient temperature. The content of the three-necked flask is poured into 250 mL of water, and the chestnut brown precipitate formed is dissolved in ethyl acetate. The organic phase is extracted, dried over magnesium sulfate, filtered, and evaporated at reduced pressure. The chestnut brown solid obtained is purified a first time in a column (support: silica 6-35 μm; eluant: CH2Cl2/MeOH/AcOEt, 97/1/2) to produce 3.29 g of product. A sample of 0.500 g is collected, then purified a second time by preparative plates (support: silica; eluant: CH2Cl2/MeOH/AcOEt, 97/1/2), to produce 0.107 mg of 2-(5-acetoxymethylfuran-2-yl)-4,9-dihydro-4,9-dioxonaphtho[2,3-d]thiazole in the form of yellow crystals. Yield: 38%; Melting point: 204° C.; Rf: 0.52 (heptane/AcOEt, 50/50); MS (I.E.): m/z 353(M+); 1H-NMR (CDCl3): δ (ppm); 8.34 (m, 1H, H-5 or H-8); 8.24 (m, 1H, H-5 or H-8); 7.81 (m, 2H, H-6, H-7); 7.41 (d, 1H, H-3', JH3'-H4'32 3.74 Hz); 6.64 (d, 1H, H-4', JH4'-H3'=3.32 Hz); 5.15 (s, 2H, CH2); 2.14 (s, 3H, CH3); 13C-NMR (CDCl3): δ (ppm); 134.39, 134.14 (2C, C-6, C-7); 133.30, 132.83 (2C, C-4a, C-8a); 127.86, 126.94 (2C, C-5, C-8); 114.52, 113.77 (2C, C-3', C-4'); 57.67 (1C, CH2); 20.83 (1C, CH3); IR (KBr): ν (cm-1); 1734, 1686 and 1669 (C=O).
  • 21
  • [ 10551-58-3 ]
  • [ 1883-75-6 ]
YieldReaction ConditionsOperation in experiment
92% With sodium tetrahydroborate In methanol at 20℃; for 0.5h;
91% Stage #1: 5-acetoxymethyl-2-furaldehyde With sodium tetrahydroborate In ethanol at 0 - 20℃; for 48h; Stage #2: With hydrogenchloride In ethanol at 0℃;
  • 22
  • [ 57-48-7 ]
  • [ 108-24-7 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
45% Stage #1: D-Fructose With acetic acid; magnesium chloride In water at 75 - 95℃; for 4.5h; Stage #2: acetic anhydride With dmap In acetic acid at 20 - 80℃; 1A Example 1A Preparation of 5-acetoxymethylfurfural Using MgCl2 107 g (0.6 mol) of D-fructose and 122 g (0.6 mol) of MgCl2.6H2O were introduced into a 2 l three-neck flask with stirring and heated to 75° C. for 30 min. The reaction mixture was admixed with 420 ml of anhydrous acetic acid (glacial acetic acid) and heated to 90-95° C. for 4 h. Thereafter, approx. 80% of the acetic acid was distilled off, the mixture was cooled to room temperature and 5 g (0.04 mol) of 4-(N,N-dimethylamino)pyridine were added. With stirring, 616 ml (6.5 mol) of acetic anhydride were added drop wise to the reaction mixture at 30-40° C., and the 600-700 ml of acetic acid were distilled off. At approx. 80° C., the reaction mixture was admixed slowly with 500 ml of water, 500 ml of MIBK and 50 g of activated carbon. After filtration through a pressure filter, the organic phase and aqueous phase were separated. The organic phase was freed of the solvent on a rotary evaporator and the residue was distilled under reduced pressure at 117-125° C./7 mbar. Yield: 45.9 g (0.27 mol, 45%) of 5-acetoxymethylfurfural.
42% Stage #1: D-Fructose In 1-methyl-pyrrolidin-2-one at 110℃; for 6h; Stage #2: acetic anhydride With dmap In 1-methyl-pyrrolidin-2-one at 20 - 25℃; for 2h; 2A Example 2A; Preparation of 5-acetoxymethylfurfural Using an Acidic Ion Exchanger; 39.4 kg (219 mol) of D-fructose and 5.9 kg of dried acidic Dowex 50WX8-200 ion exchanger (styrene-divinylbenzene copolymer resin with SO3H groups, obtainable from The Dow Chemical Company, Midland, U.S.A.) in the H form were introduced with stirring into 90 l of NMP and heated to 110° C. for 6 h. After cooling, the reaction mixture was filtered and washed with 8 l of NMP. The filtrate was admixed with stirring with 390 g (3.2 mol) of 4-(N,N-dimethylamino)pyridine and 20.5 1 (217 mol) of acetic anhydride at 20-25° C. within 1 h. After continuing the reaction for 1 h, the brown reaction mixture was freed of the solvent at 90-100° C. under reduced pressure (of 50-10 mbar). After cooling, the residue was admixed with 160 l of MtBE, 60 1 of water and 4 kg of activated carbon. The suspension was filtered though Celite. After the phase separation, the solvent of the filtrate was distilled off at 50° C. under reduced pressure (20 mbar) and the residue was fractionally distilled under reduced pressure at 106-110° C./5 mbar.Yield: 15.5 kg (92 mol, 42%) of 5-acetoxymethylfurfural
  • 23
  • [ 10551-58-3 ]
  • [ 152932-55-3 ]
YieldReaction ConditionsOperation in experiment
66% With diethylamino-sulfur trifluoride In dichloromethane at 0 - 20℃; for 16h; 8.1 Step 1: [5-(Difluoromethyl)-2-furyl]methyl acetate Step 1: [5-(Difluoromethyl)-2-furyl]methyl acetate 5-Acetoxymethyl-2-furaldehyde (3.0 g, 18 mmol) was dissolved in DCM (50 mL) and diethylaminosulfur trifluoride (DAST) (4.3 g, 27 mmol) was added to the solution at 0 °C. The reaction mixture was then allowed to warm to rt and stir for 16 h. The mixture was then quenched with water and extracted with DCM (50 mL). The organic layer was concentrated and the resulting residue was purified on silica gel to give [5-(difluoromethyl)-2-furyl]methyl acetate (2.2 g, 66%).
55% With diethylamino-sulfur trifluoride In dichloromethane at 0 - 20℃; for 20h; 18.A PREPARATION 18; Preparation of (5-(difluoroniethyl)furan-2-yl)niethanamine; A. To the solution of (5-formylfuran-2-yl)methyl acetate (6.70 g, 39.8 mmol) in anhydrous dichloromethane (50 mL) was added dropwise (diethylamino)sulfur trifluoride (5.22 mL, 39.85 mmol) at O0C. The reaction mixture was stirred at ambient temperature for 20 hours, quenched with saturated sodium bicarbonate solution and extracted with dichloromethane (3 x 50 mL). The organic solutions were combined, dried over anhydrous sodium sulphate, filtered and concentrated in vacuo. The residue was purified by column chromatography eluted with ethyl acetate/hexane (3/7) to afford (5- (difluoromethyl)furan-2-yl)methyl acetate as a colorless oil in 55% yield (4.21 g): 1H NMR (300 MHz, CDCl3) δ 6.61 -6.59 (m, I H), 5.57 (t, JH.F = 54.4 Hz, I H), 6.45-6.30 (m, I H), 5.04 (s, 2H), 2.07 (s, 3H).
With diethylamino-sulfur trifluoride In dichloromethane Inert atmosphere;
  • 24
  • [ 57-48-7 ]
  • [ 64-19-7 ]
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
1: 22.3% 2: 71.5% In 1-ethyl-3-methyl-1H-imidazol-3-ium chloride at 100℃; for 3h; 1 Example 1In a" batch experiment, 50 mg of substrate (glucose or fructose) and 250 mg of 1-Ethyl-3- methylimidazolium chloride (EMIM) or 500 mg of a mixture of EMIM and H-3- methylimidazolium bis(trifluoromethanesulfonyl)imide (HMIM) were loaded in a Teflon lined reactor with 7.5 ml volume. 1 ml of acetic acid was added and the mixture reacted under nitrogen (12.5 bar) in the presence of CrCI2 as catalyst for 3 h at 100 0C. Two products were observed in the UV spectra and identified as HMF and 5-acetoxy methyl furfural (AMF). Selectivities and conversions for catalysts used in this example can be found in table below.The substrate conversions and the selectivities and yields were calculated according to the formulas:Conversion = 100* [n0 (substrate) - nt (substrate)] / n0 substrate Selectivity = 100 * nt (product) / [n0 (substrate) - nt (substrate)]Yield = 100 * nt (product) / n0 substrate,Where: n0- the initial number of moles nt- the number the moles of a compound at time "t".
1: 19.6% 2: 59.4% In H-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; 1-ethyl-3-methyl-1H-imidazol-3-ium chloride at 100℃; for 3h; 1 Example 1In a" batch experiment, 50 mg of substrate (glucose or fructose) and 250 mg of 1-Ethyl-3- methylimidazolium chloride (EMIM) or 500 mg of a mixture of EMIM and H-3- methylimidazolium bis(trifluoromethanesulfonyl)imide (HMIM) were loaded in a Teflon lined reactor with 7.5 ml volume. 1 ml of acetic acid was added and the mixture reacted under nitrogen (12.5 bar) in the presence of CrCI2 as catalyst for 3 h at 100 0C. Two products were observed in the UV spectra and identified as HMF and 5-acetoxy methyl furfural (AMF). Selectivities and conversions for catalysts used in this example can be found in table below.The substrate conversions and the selectivities and yields were calculated according to the formulas:Conversion = 100* [n0 (substrate) - nt (substrate)] / n0 substrate Selectivity = 100 * nt (product) / [n0 (substrate) - nt (substrate)]Yield = 100 * nt (product) / n0 substrate,Where: n0- the initial number of moles nt- the number the moles of a compound at time "t".
  • 25
  • [ 492-62-6 ]
  • [ 64-19-7 ]
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
1: 1.8% 2: 6.9% In H-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; 1-ethyl-3-methyl-1H-imidazol-3-ium chloride at 100℃; for 3h; 1 Example 1In a" batch experiment, 50 mg of substrate (glucose or fructose) and 250 mg of 1-Ethyl-3- methylimidazolium chloride (EMIM) or 500 mg of a mixture of EMIM and H-3- methylimidazolium bis(trifluoromethanesulfonyl)imide (HMIM) were loaded in a Teflon lined reactor with 7.5 ml volume. 1 ml of acetic acid was added and the mixture reacted under nitrogen (12.5 bar) in the presence of CrCI2 as catalyst for 3 h at 100 0C. Two products were observed in the UV spectra and identified as HMF and 5-acetoxy methyl furfural (AMF). Selectivities and conversions for catalysts used in this example can be found in table below.The substrate conversions and the selectivities and yields were calculated according to the formulas:Conversion = 100* [n0 (substrate) - nt (substrate)] / n0 substrate Selectivity = 100 * nt (product) / [n0 (substrate) - nt (substrate)]Yield = 100 * nt (product) / n0 substrate,Where: n0- the initial number of moles nt- the number the moles of a compound at time "t".
1: 1.3% 2: 5.1% In 1-ethyl-3-methyl-1H-imidazol-3-ium chloride at 100℃; for 3h; 1 Example 1In a" batch experiment, 50 mg of substrate (glucose or fructose) and 250 mg of 1-Ethyl-3- methylimidazolium chloride (EMIM) or 500 mg of a mixture of EMIM and H-3- methylimidazolium bis(trifluoromethanesulfonyl)imide (HMIM) were loaded in a Teflon lined reactor with 7.5 ml volume. 1 ml of acetic acid was added and the mixture reacted under nitrogen (12.5 bar) in the presence of CrCI2 as catalyst for 3 h at 100 0C. Two products were observed in the UV spectra and identified as HMF and 5-acetoxy methyl furfural (AMF). Selectivities and conversions for catalysts used in this example can be found in table below.The substrate conversions and the selectivities and yields were calculated according to the formulas:Conversion = 100* [n0 (substrate) - nt (substrate)] / n0 substrate Selectivity = 100 * nt (product) / [n0 (substrate) - nt (substrate)]Yield = 100 * nt (product) / n0 substrate,Where: n0- the initial number of moles nt- the number the moles of a compound at time "t".
  • 26
  • D-fructose [ No CAS ]
  • [ 64-19-7 ]
  • [ 67-47-0 ]
  • [ 64-18-6 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
39.4914% In water at 80℃; 1; 2 Example 1; The conventional method for synthesizing HMF and AcHMF from fructose includes a batch reaction on an autoclave (Parr) reactor followed by a separate step for purification. As shown in FIG. 1, the temperature control 2 controls both the temperature of the reaction mixture and the heating jacket in the autoclave reactor 1. A heating jacket (not shown) is used to heat the reaction. The pressure gauge 3 shows if the reaction is creating gas, or monitors the pressure on the vessel if it was applied. The speed control 4 is for the stirring mechanism. Stirring is necessary to keep the reaction mixture in contact with all necessary materials. The sample port 5 allows the scientist to retrieve samples and specific points during the reaction to monitor for progress. Reactants must be in solution before being put into a reactor vessel.The reaction conditions for the autoclave reactions were varied to test the effect of different reaction conditions. The reactions were performed in the 100 mL capacity Parr reactor. About 20 grams of High fructose corn syrup (HFCS) is added to each reaction. Three different temperatures: 110°, 125°, and 150° Celsius were tested with and without an ion exchange resin. The resin of choice was Amberlyst 35 exchange. Results are shown in Table 1.As can be seen in Table 1 above, AcHMF was formed in the largest amount in Comparative Example No.4 at 150° C. using a resin in an autoclave reactor as shown in FIG. 2. In a 100 mL capacity Parr reactor, 6.7799 g of fructose and 23.79 g of HFCS in solution was heated to 150° C. The AcHMF yield was 0.2331 in Comparative Example No.4.In these examples of Example 1, a first method of production of substantially pure HMF uses packed columns. Two different types of columns were used to produce and purify HMF. Each column, however, was packed with a cation exchange resin, which had been soaked in the desired solvent, then loaded to a heated column once the resin had appropriately expanded. A cation exchange resin is an ion exchange resin that adds protons to the reaction. The water content of the resin used ranged from less than about 20%, to less than about 10% in order to prevent the rehydration of HMF. The results of the columns are shown in FIG. 3. The major product was HMF with the remainder being unreacted fructose. In this example, the Amberlyst 35 exchange resin performed best of all columns tested, including the gravity flow columns.Maximal reaction conditions included 80° C. in a column packed with the Amberlyst 35 ion exchange resin and acetic acid, providing a yield of AcHMF is approximately 0.395 moles. Columns performed more consistently than the conventional batch reactions, which may be due to a number of reasons. Product stays longer on the resin in a chromatography column, and a larger amount of the resin remains in the column than in the batch reactions. There is also better control of the temperature in the column due to the heated jacketed column.Samples marked with (*) in Table 2 are comparative examples. The comparative examples include batch reactions. The temperatures in the autoclave varied from approximately 105° C.-155° C. in the course of the reaction. The reaction mixture from the columns could also be fed back through for another pass, which will further increase the yield of the desired product. The yield is lower during a batch reaction when it is run at a higher temperature, such as 125° C., compared to a pulse reaction at 80° C. and a gravity column reaction at 90° C. The yield in the batch reaction using Amberlyst 35 having a temperature of 150° C. is increased due to the high temperature.; Example 2The graph shown in FIG. 4 illustrates the results of the pulse resin test at 80° C. where the flow rate was set at about 1.48 mL/min. for the first 33 minutes and about 1.36 mL/min. after the 33rd minute until completion of the reaction at about 63 minutes. After approximately 30 minutes, 0.07 moles of AcHMF was eluted, compared to a mole fraction of approximately 0.0006 for the starting material, fructose. The byproducts, levulinic and formic acids, are also measured. No measurable levulinic acid was found during the synthesis of AcHMF.
  • 27
  • D-fructose [ No CAS ]
  • [ 64-19-7 ]
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
1: 41% 2: 28% at 110 - 125℃; for 2 - 3h; 4; 5 Example 4; Preparation of 5-Acetoxymethylfurfural (ACHMF) from FructoseCrystalline fructose (18 g) is placed in a 100 mL reaction vessel with acetic acid (50 g) and Amberlyst 15 resin (4 g). The solution is heated to 110° C. for 3 hours with samples collected regularly. Analytical results and HPLC trace confirm the formation of AcHMF. Analysis of the product mixture indicated a solution of 9.89% AcHMF and 5.14% HMF for a 41% yield of AcHMF and 28% yield of HMF. The yields disclosed herein are exemplary only and do not necessarily reflect the optimal yields possible when reaction conditions are optimized. HPLC trace confirmed formation of AcHMF, (see FIG. 4).; Example 5; Synthesis and Purification of AcHMF from FructoseCrystalline fructose (180 g) is placed in a 1 L reaction vessel with acetic acid (500 g) and Amberlyst 15 resin (40 g). The solution is heated to 125° C. for 2 hours. NMR and analytical results indicates the formation of AcHMF. The solution is filtered to remove the resin catalyst and acetic acid is removed by rotary evaporation. AcHMF is collected by extraction with methyl t-butyl ether. The crude material is subjected to simple distillation (115° C., 3 torr) to provide AcHMF as orange crystals. HPLC trace confirms AcHMF formation, (see FIG. 5), and 1H NMR analysis indicates substantially pure AcHMF. NMR (δ, 1 H): 9.70 (s, 1.0 H); 7.40 (s, 1.0 H); 6.80 (s, 1.0 H); 5.10 (s, 2.0 H); 2.10 (s, 3.0H). See FIG. 1.
1: 7.63925% 2: 31.25% In water at 110 - 150℃; 1.1; 1.3; 1.4 Example 1; The conventional method for synthesizing HMF and AcHMF from fructose includes a batch reaction on an autoclave (Parr) reactor followed by a separate step for purification. As shown in FIG. 1, the temperature control 2 controls both the temperature of the reaction mixture and the heating jacket in the autoclave reactor 1. A heating jacket (not shown) is used to heat the reaction. The pressure gauge 3 shows if the reaction is creating gas, or monitors the pressure on the vessel if it was applied. The speed control 4 is for the stirring mechanism. Stirring is necessary to keep the reaction mixture in contact with all necessary materials. The sample port 5 allows the scientist to retrieve samples and specific points during the reaction to monitor for progress. Reactants must be in solution before being put into a reactor vessel.The reaction conditions for the autoclave reactions were varied to test the effect of different reaction conditions. The reactions were performed in the 100 mL capacity Parr reactor. About 20 grams of High fructose corn syrup (HFCS) is added to each reaction. Three different temperatures: 110°, 125°, and 150° Celsius were tested with and without an ion exchange resin. The resin of choice was Amberlyst 35 exchange. Results are shown in Table 1.As can be seen in Table 1 above, AcHMF was formed in the largest amount in Comparative Example No.4 at 150° C. using a resin in an autoclave reactor as shown in FIG. 2. In a 100 mL capacity Parr reactor, 6.7799 g of fructose and 23.79 g of HFCS in solution was heated to 150° C. The AcHMF yield was 0.2331 in Comparative Example No.4.In these examples of Example 1, a first method of production of substantially pure HMF uses packed columns. Two different types of columns were used to produce and purify HMF. Each column, however, was packed with a cation exchange resin, which had been soaked in the desired solvent, then loaded to a heated column once the resin had appropriately expanded. A cation exchange resin is an ion exchange resin that adds protons to the reaction. The water content of the resin used ranged from less than about 20%, to less than about 10% in order to prevent the rehydration of HMF. The results of the columns are shown in FIG. 3. The major product was HMF with the remainder being unreacted fructose. In this example, the Amberlyst 35 exchange resin performed best of all columns tested, including the gravity flow columns.Maximal reaction conditions included 80° C. in a column packed with the Amberlyst 35 ion exchange resin and acetic acid, providing a yield of AcHMF is approximately 0.395 moles. Columns performed more consistently than the conventional batch reactions, which may be due to a number of reasons. Product stays longer on the resin in a chromatography column, and a larger amount of the resin remains in the column than in the batch reactions. There is also better control of the temperature in the column due to the heated jacketed column.Samples marked with (*) in Table 2 are comparative examples. The comparative examples include batch reactions. The temperatures in the autoclave varied from approximately 105° C.-155° C. in the course of the reaction. The reaction mixture from the columns could also be fed back through for another pass, which will further increase the yield of the desired product. The yield is lower during a batch reaction when it is run at a higher temperature, such as 125° C., compared to a pulse reaction at 80° C. and a gravity column reaction at 90° C. The yield in the batch reaction using Amberlyst 35 having a temperature of 150° C. is increased due to the high temperature.
1: 1.9697% 2: 16.63% In water at 110 - 150℃; 1.2; 1.5 Example 1; The conventional method for synthesizing HMF and AcHMF from fructose includes a batch reaction on an autoclave (Parr) reactor followed by a separate step for purification. As shown in FIG. 1, the temperature control 2 controls both the temperature of the reaction mixture and the heating jacket in the autoclave reactor 1. A heating jacket (not shown) is used to heat the reaction. The pressure gauge 3 shows if the reaction is creating gas, or monitors the pressure on the vessel if it was applied. The speed control 4 is for the stirring mechanism. Stirring is necessary to keep the reaction mixture in contact with all necessary materials. The sample port 5 allows the scientist to retrieve samples and specific points during the reaction to monitor for progress. Reactants must be in solution before being put into a reactor vessel.The reaction conditions for the autoclave reactions were varied to test the effect of different reaction conditions. The reactions were performed in the 100 mL capacity Parr reactor. About 20 grams of High fructose corn syrup (HFCS) is added to each reaction. Three different temperatures: 110°, 125°, and 150° Celsius were tested with and without an ion exchange resin. The resin of choice was Amberlyst 35 exchange. Results are shown in Table 1.As can be seen in Table 1 above, AcHMF was formed in the largest amount in Comparative Example No.4 at 150° C. using a resin in an autoclave reactor as shown in FIG. 2. In a 100 mL capacity Parr reactor, 6.7799 g of fructose and 23.79 g of HFCS in solution was heated to 150° C. The AcHMF yield was 0.2331 in Comparative Example No.4.In these examples of Example 1, a first method of production of substantially pure HMF uses packed columns. Two different types of columns were used to produce and purify HMF. Each column, however, was packed with a cation exchange resin, which had been soaked in the desired solvent, then loaded to a heated column once the resin had appropriately expanded. A cation exchange resin is an ion exchange resin that adds protons to the reaction. The water content of the resin used ranged from less than about 20%, to less than about 10% in order to prevent the rehydration of HMF. The results of the columns are shown in FIG. 3. The major product was HMF with the remainder being unreacted fructose. In this example, the Amberlyst 35 exchange resin performed best of all columns tested, including the gravity flow columns.Maximal reaction conditions included 80° C. in a column packed with the Amberlyst 35 ion exchange resin and acetic acid, providing a yield of AcHMF is approximately 0.395 moles. Columns performed more consistently than the conventional batch reactions, which may be due to a number of reasons. Product stays longer on the resin in a chromatography column, and a larger amount of the resin remains in the column than in the batch reactions. There is also better control of the temperature in the column due to the heated jacketed column.Samples marked with (*) in Table 2 are comparative examples. The comparative examples include batch reactions. The temperatures in the autoclave varied from approximately 105° C.-155° C. in the course of the reaction. The reaction mixture from the columns could also be fed back through for another pass, which will further increase the yield of the desired product. The yield is lower during a batch reaction when it is run at a higher temperature, such as 125° C., compared to a pulse reaction at 80° C. and a gravity column reaction at 90° C. The yield in the batch reaction using Amberlyst 35 having a temperature of 150° C. is increased due to the high temperature.
  • 28
  • [ 10551-58-3 ]
  • tetrahydrofuran-2,5-dimethanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With hydrogen at 170 - 195℃; for 2h; 8 Example 8Reduction of 5-Acetoxymethylfurfural (AcHMF); A reaction mixture containing AcHMF (5.0 g) and ethanol (50 mL) is charged into a 100 mL reaction vessel. The G-69B catalyst may be obtained from Sub Chemie, Louisville, Ky. (0.50 g) is added to the vessel. The vessel is purged with hydrogen (4×500 psi) with stirring (1000 rpm). The vessel is then pressurized to 600 psi and heated to 170° C. with continual stirring. After 1 hour, the reaction is allowed to heat to 195° C. for an additional hour. The reaction is then allowed to cool to room temperature and the catalyst removed by vacuum filtration. Most of the solvent is removed by rotary evaporation to provide yellow oil (16.97 g). The UV analysis (λ=284 nm) does not show the presence of AcHMF, indicating complete conversion of AcHMF to 2,5-dihydroxymethyltetrahydrofuran.
Multi-step reaction with 2 steps 1.1: sodium tetrahydroborate / ethanol / 48 h / 0 - 20 °C 1.2: 0 °C / pH 4 2.1: hydrogen / nickel / ethanol / 20 °C / 1500.15 Torr
  • 29
  • [ 10551-58-3 ]
  • [ 3238-40-2 ]
YieldReaction ConditionsOperation in experiment
90.2% With oxygen; acetic acid at 130℃; for 2h; Autoclave; 2b Examples Set 1; In Examples 1a-3d, glacial acetic acid and the catalyst components in concentrations described in Tables 1, 2 and 3 were transferred to a 300 mL titanium autoclave equipped with a high pressure condenser, a baffle and an Isco pump. Cobalt, manganese and ionic bromine were provided as cobalt (II) acetate tetrahydrate, manganese (II) acetate and sodium bromide and/or aqueous hydrobromic acid respectively. The autoclave was pressurized with approximately 50 psig of nitrogen and the homogeneous mixture was heated to the desired temperature in a closed system (i.e., with no gas flow) with stirring. At reaction temperature, an air flow of 1500 sccm was introduced at the bottom of the solution and the reaction pressure was adjusted to the desired pressure. A solution of 5-HMF/5-AMF/5-EMF in acetic acid was fed to the mixture at a rate of 0.833 mL/min via a high pressure Isco pump (this is t=0 for the reaction time). After 30 seconds from the start of substrate feeding, 1.0 g of peracetic acid in 5.0 mL of acetic acid was introduced using a blow-case to start the reaction. The feed was stopped after 1 h and the reaction continued for an additional hour at the same conditions of air flow, temperature and pressure. After the reaction time was completed, the air flow was stopped and the autoclave was cooled to room temperature and depressurized. The heterogeneous mixture was filtered to isolate the crude FDCA. The mass of the filtrate was recorded. The crude FDCA was washed with 60 mL of acetic acid two times and then twice with 100 mL of DI water. The washed crude FDCA was oven dried at 110° C. under vacuum overnight and then weighed. The solid and the filtrate were analyzed by Gas Chromatography using BSTFA derivatization method.The Off-gas was analyzed for CO and CO2 by ND-1R (ABB, Advanced Optima) and O2 by a paramagnetism detection system (Servomex, 1440 Model).
90.2% With oxygen; acetic acid at 130℃; for 2h; Autoclave; 2b Examples Set 1; In Examples 1a-3d, glacial acetic acid and the catalyst components in concentrations described in Tables 1, 2 and 3 were transferred to a 300 mL titanium autoclave equipped with a high pressure condenser, a baffle and an Isco pump. Cobalt, manganese and ionic bromine were provided as cobalt (II) acetate tetrahydrate, manganese (II) acetate and sodium bromide and/or aqueous hydrobromic acid respectively. The autoclave was pressurized with approximately 50 psig of nitrogen and the homogeneous mixture was heated to the desired temperature in a closed system (i.e., with no gas flow) with stirring. At reaction temperature, an air flow of 1500 sccm was introduced at the bottom of the solution and the reaction pressure was adjusted to the desired pressure. A solution of 5-HMF/5-AMF/5-EMF in acetic acid was fed to the mixture at a rate of 0.833 mL/min via a high pressure Isco pump (this is t=0 for the reaction time). After 30 seconds from the start of substrate feeding, 1.0 g of peracetic acid in 5.0 mL of acetic acid was introduced using a blow-case to start the reaction. The feed was stopped after 1 h and the reaction continued for an additional hour at the same conditions of air flow, temperature and pressure. After the reaction time was completed, the air flow was stopped and the autoclave was cooled to room temperature and depressurized. The heterogeneous mixture was filtered to isolate the crude FDCA. The mass of the filtrate was recorded. The crude FDCA was washed with 60 mL of acetic acid two times and then twice with 100 mL of DI water. The washed crude FDCA was oven dried at 110° C. under vacuum overnight and then weighed. The solid and the filtrate were analyzed by Gas Chromatography using BSTFA derivatization method.The Off-gas was analyzed for CO and CO2 by ND-1R (ABB, Advanced Optima) and O2 by a paramagnetism detection system (Servomex, 1440 Model).
90.2% With manganese; oxygen; cobalt; acetic acid at 130℃; 2.b EXAMPLES General procedure: Air oxidation of 5-HMF/5-AMF/5-EMF using cobalt, manganese and ionic bromine catalysts system in acetic acid solvent were conducted. After reaction the heterogeneous mixture was filtered to isolate the crude FDCA. The crude FDCA was washed with acetic acid two times and then twice with DI water. The washed crude FDCA was oven dried at 110° C. under vacuum overnight. The solid and the filtrate were analyzed by Gas Chromatography using BSTFA derivatization method. b* of the solid was measured using a Hunter Ultrascan XE instrument. The Off-gas was analyzed for CO and CO2 by ND-1R (ABB, Advanced Optima) and O2 by a paramagnetism detection system (Servomex, 1440 Model).
90.2% With oxygen; acetic acid at 130℃; 2a; 2b General procedure: Air oxidation of 5-HMF/5-AMF/5-EMF using cobalt, manganese and ionic bromine catalysts system in acetic acid solvent were conducted. After reaction the heterogeneous mixture was filtered to isolate the crude FDCA. The crude FDCA was washed with acetic acid two times and then twice with DI water. The washed crude FDCA was oven dried at 110° C. under vacuum overnight. The solid and the filtrate were analyzed by Gas Chromatography using BSTFA derivatization method. b* of the solid was measured using a Hunter Ultrascan XE instrument. As shown in Tables 1 to 3 we have discovered conditions that to generate yields of FDCA up to 89.4%, b*<6, and low carbon burn (<0.00072 mol/min CO+CO2)
90.2% With manganese; oxygen; cobalt; acetic acid at 130℃; 2b General procedure: Air oxidation of 5-HMF/5-AMF/5-EMF using cobalt, manganese and ionic bromine catalysts system in acetic acid solvent were conducted. After reaction the heterogeneous mixture was filtered to isolate the crude FDCA. The crude FDCA was washed with acetic acid two times and then twice with DI water. The washed crude FDCA was oven dried at 110° C. under vacuum overnight. The solid and the filtrate were analyzed by Gas Chromatography using BSTFA derivatization method. b* of the solid was measured using a Hunter Ultrascan XE instrument. As shown in Tables 1 to 3 we have discovered conditions that to generate yields of FDCA up to 89.4%, b*<6, and low carbon burn (<0.00072 mol/min CO+CO2)
82% With 10 wt% platinum on carbon; water; oxygen; sodium hydrogencarbonate at 70℃; for 2h;
54% With oxygen; acetic acid; sodium bromide at 100℃; for 2h; 7 Example 7Oxidation of 5-Acetoxymethylfurfural (AcHMF) to 2,5-Furandicarboxylic Acid (FDCA); A reaction mixture containing AcHMF (5.0 g), acetic acid (50 mL), cobalt acetate (0.132 g), manganese acetate (0.135 g), and sodium bromide (0.114 g) is placed in a 100 mL reactor and subjected to 500-800 psi oxygen at 100° C. for 2 hours. Upon filtration and evaporation of the solvent, 2.53 g of tan solid is isolated. 1H NMR indicates substantially pure FDCA. The overall yield of FDCA from AcHMF is 54%. See FIG. 3.
64.82 %Chromat. With oxygen; acetic acid at 180℃; for 1h; 1d Example 1Example 1 shows the selectivity of FDCA in the oxidation of HMF, of a HMF/AMF 3/2 mixture, of a HMF/AMF 2/3 mixture and of AMF, respectively, with 2.7 mol% Co catalyst (relative to substrate), and Co/Mn molar ratio of 1/1 , so that the catalyst concentration (Co + Mn) amounted to 5.4 mol%. The Br/(Co+Mn) molar ratio was 1 .0; 0.7; 0.4 and 0.1 at 0.26 M substrate concentration in acetic acid at 180 °C for 1 hr with 20 bar air. The amount of oxygen was 2.69 mol oxygen per mol substrate. Under these conditions, higher Br amounts give higher yields but when Br/(Co+Mn) > 1 , corrosion will be a problem on commercial scale. HMF gives slightly higher yields than AMF at one hour reaction time. The results of these experiments are given in Table 1 .
Multi-step reaction with 3 steps 1: indium(III) triflate; trimethyl orthoformate / dichloromethane / 20 °C 2: methanol; sodium carbonate / dichloromethane 3: sodium carbonate; oxygen / water / 15 h / 130 °C / 3800.26 Torr
Multi-step reaction with 3 steps 1: trimethyl orthoformate; indium(III) triflate / dichloromethane / 15 h / 20 °C 2: sodium carbonate; water / ethanol / 5 h / 20 °C 3: sodium carbonate; oxygen / water / 139.84 °C / 3750.38 Torr / Autoclave
Multi-step reaction with 4 steps 1: trimethyl orthoformate; indium(III) triflate / dichloromethane / 15 h / 20 °C 2: sodium carbonate; water / ethanol / 5 h / 20 °C 3: sodium carbonate / 139.84 °C / 750.08 Torr / Autoclave 4: sodium carbonate; oxygen / water / 15 h / 139.84 °C / 3750.38 Torr / Autoclave
Multi-step reaction with 4 steps 1: trimethyl orthoformate; indium(III) triflate / dichloromethane / 15 h / 20 °C 2: sodium carbonate; water / ethanol / 5 h / 20 °C 3: sodium carbonate; oxygen / water / 15 h / 139.84 °C / 3750.38 Torr / Autoclave 4: sodium carbonate; oxygen / water / 15 h / 139.84 °C / 3750.38 Torr / Autoclave
Multi-step reaction with 4 steps 1: trimethyl orthoformate; indium(III) triflate / dichloromethane / 15 h / 20 °C 2: sodium carbonate; water / ethanol / 5 h / 20 °C 3: sodium carbonate; oxygen / water-d2 / 0.5 h / 139.84 °C / 3750.38 Torr / Autoclave 4: sodium carbonate; oxygen / water / 15 h / 139.84 °C / 3750.38 Torr / Autoclave
Multi-step reaction with 4 steps 1: trimethyl orthoformate; indium(III) triflate / dichloromethane / 15 h / 20 °C 2: sodium carbonate; water / ethanol / 5 h / 20 °C 3: sodium carbonate; oxygen / water-d2 / 8 h / 139.84 °C / 3750.38 Torr / Autoclave 4: sodium carbonate; oxygen / water / 15 h / 139.84 °C / 3750.38 Torr / Autoclave
With potassium permanganate; water; sodium hydroxide at 20℃; 2.1; 2-1-2-12 1) Oxidation of AMF AMF (10g, 59.3mmol) synthesized in Preparation Example 1 was put into a 250mL flask, and H2O (150mL) was added thereto.After adding NaOH (16.6g, 415.4 mmol) to thereaction solution, KMnO4(22.5 g, 142.4 mmol) is carefully added.After stirring for at least 18 hours at room temperature and general atmospheric conditions, the reaction solution is filtered.Conc HCl was added to the filtrate to lower the pH to 1 or less, and the resulting brown solid was filtered.The filtered solid was washed with H2O and then dried under vacuum without further purification (HPLC purity: >99%).

Reference: [1]Current Patent Assignee: EASTMAN CHEMICAL CO - US2012/302768, 2012, A1 Location in patent: Page/Page column 9-10
[2]Current Patent Assignee: EASTMAN CHEMICAL CO - US2012/302770, 2012, A1 Location in patent: Page/Page column 8-10 Current Patent Assignee: EASTMAN CHEMICAL CO - US2012/302771, 2012, A1 Location in patent: Page/Page column 8-10 Current Patent Assignee: EASTMAN CHEMICAL CO - US2012/302772, 2012, A1 Location in patent: Page/Page column 8-10 Current Patent Assignee: EASTMAN CHEMICAL CO - US2012/302773, 2012, A1 Location in patent: Page/Page column 8-10
[3]Current Patent Assignee: EASTMAN CHEMICAL CO - US2014/66639, 2014, A1 Location in patent: Paragraph 0064; 0065
[4]Current Patent Assignee: EASTMAN CHEMICAL CO - US10344011, 2019, B1 Location in patent: Page/Page column 15; 16
[5]Current Patent Assignee: EASTMAN CHEMICAL CO - US2019/337914, 2019, A1 Location in patent: Page/Page column 8-9
[6]Kang, Eun-Sil; Hong, Yeon-Woo; Chae, Da Won; Kim, Bora; Kim, Baekjin; Kim, Yong Jin; Cho, Jin Ku; Kim, Young Gyu [ChemSusChem, 2015, vol. 8, # 7, p. 1179 - 1188]
[7]Current Patent Assignee: ARCHER-DANIELS-MIDLAND CO - US2009/156841, 2009, A1 Location in patent: Page/Page column 10
[8]Current Patent Assignee: AVANTIUM N.V. - WO2011/43661, 2011, A1 Location in patent: Page/Page column 6-9
[9]Current Patent Assignee: Mitsubishi Chemical Corp (in: MCHC Group); HOKKAIDO UNIVERSITY; MITSUBISHI CHEMICAL HOLDINGS CORPORATION - JP2018/39778, 2018, A
[10]Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J. M.; Nakajima, Kiyotaka [Angewandte Chemie - International Edition, 2018, vol. 57, # 27, p. 8235 - 8239][Angew. Chem., 2018, p. 8367 - 8371,5]
[11]Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J. M.; Nakajima, Kiyotaka [Angewandte Chemie - International Edition, 2018, vol. 57, # 27, p. 8235 - 8239][Angew. Chem., 2018, p. 8367 - 8371,5]
[12]Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J. M.; Nakajima, Kiyotaka [Angewandte Chemie - International Edition, 2018, vol. 57, # 27, p. 8235 - 8239][Angew. Chem., 2018, p. 8367 - 8371,5]
[13]Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J. M.; Nakajima, Kiyotaka [Angewandte Chemie - International Edition, 2018, vol. 57, # 27, p. 8235 - 8239][Angew. Chem., 2018, p. 8367 - 8371,5]
[14]Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J. M.; Nakajima, Kiyotaka [Angewandte Chemie - International Edition, 2018, vol. 57, # 27, p. 8235 - 8239][Angew. Chem., 2018, p. 8367 - 8371,5]
[15]Current Patent Assignee: UNI PLUS - KR2021/72855, 2021, A Location in patent: Paragraph 0120-0123; 0132; 0136
  • 30
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
  • [ 3238-40-2 ]
YieldReaction ConditionsOperation in experiment
With oxygen; acetic acid; sodium bromide at 100℃; for 1h; 9 Example 9 Oxidation of a Mixture of HMF and HMF Ester to FDCA; A product mixture composed of predominantly HMF ester with residual HMF in acetic acid is subjected to oxidation with the addition of cobalt acetate, manganese acetate, and sodium bromide. This mixture is pressurized with oxygen and heated to over 100° C. for over an hour. Upon filtration and evaporation, a product of FDCA is isolated.
77.66 %Chromat. With oxygen; acetic acid at 180℃; for 1h; 1c Example 1Example 1 shows the selectivity of FDCA in the oxidation of HMF, of a HMF/AMF 3/2 mixture, of a HMF/AMF 2/3 mixture and of AMF, respectively, with 2.7 mol% Co catalyst (relative to substrate), and Co/Mn molar ratio of 1/1 , so that the catalyst concentration (Co + Mn) amounted to 5.4 mol%. The Br/(Co+Mn) molar ratio was 1 .0; 0.7; 0.4 and 0.1 at 0.26 M substrate concentration in acetic acid at 180 °C for 1 hr with 20 bar air. The amount of oxygen was 2.69 mol oxygen per mol substrate. Under these conditions, higher Br amounts give higher yields but when Br/(Co+Mn) > 1 , corrosion will be a problem on commercial scale. HMF gives slightly higher yields than AMF at one hour reaction time. The results of these experiments are given in Table 1 .
  • 31
  • [ 10551-58-3 ]
  • (4S)-5,5-dimethyl-3-[(2S)-2-[4'-(1,3-oxazol-5-yl)biphenyl-4-yl]methoxy}propanoyl]-4-phenyl-1,3-oxazolidin-2-one [ No CAS ]
  • {5-[(1S,2S)-3-[(4S)-5,5-dimethyl-2-oxo-4-phenyl-1,3-oxazolidin-3-yl]-1-hydroxy-2-methyl-2-[4'-(1,3-oxazol-5-yl)biphenyl-4-yl]methoxy}-3-oxopropyl]-2-furyl}methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
8% Stage #1: (4S)-5,5-dimethyl-3-[(2S)-2-[4'-(1,3-oxazol-5-yl)biphenyl-4-yl]methoxy}propanoyl]-4-phenyl-1,3-oxazolidin-2-one With lithium diisopropyl amide In tetrahydrofuran; n-heptane; ethylbenzene at -78℃; for 0.5h; Inert atmosphere; Stage #2: With triisopropoxytitanium(IV) chloride In tetrahydrofuran; n-heptane; ethylbenzene at -78 - -40℃; Inert atmosphere; Stage #3: 5-acetoxymethyl-2-furaldehyde In tetrahydrofuran; n-heptane; ethylbenzene at -78 - -40℃; Inert atmosphere; 46.2 Step 2 Preparation of {5-[(1S,2S)-3-[(4S)-5,5t-(1 ,3-oxazol-5-yl)bιphenyl-4-yf]methoxy}-3- oxopropyl)-2-fυryl}methy. acetate (C82). A solution of lithium ditsopropylamide in heptane/tetrahydrofuran/ethylbenzene (2.0 M1 0 71 mL) was cooled to -78°C and treated with a cold solution (-78°C) of compound C83 (500 mg, 1.01 mmol) in tetrahydrofuran (5 mL) The reaction mixture was stirred at -78°C for an additional 30 minutes and slowly treated with chlorotitanium triisopropoxide (1 M in hexanes, 4 05 mL). The mixture was then stirred at - 40°C for an additional 1 hour The reaction mixture was cooled to -78°C and slowly treated with a solution of (5-formy.furan-2-y.)methy. acetate (220 mg, 1 31) in tetrahydrofuran (2 mL). The mixture was then warmed to -4O°C and stiired for an additional 2 hours. The teaction mixture was quenched with saturated aqueous ammonium chlonde solution, diluted with tetrahydrofuran (10 mL), stirred with Celite for 1 hour, and filtered The resultant filtrate was concentrated, and the residue was punfied by silica gel chromatography (gradient: 95' 5 hexane. ethyl acetate to 65 35 hexane.ethyl acetate) to provide C82 as a white solid Yield: 51 mg, 8%. MS (APCI) m/z 665 5 (M + 1)
  • 32
  • [ 10551-58-3 ]
  • [ 6126-49-4 ]
YieldReaction ConditionsOperation in experiment
89 %Spectr. With palladium on carbon; hydrogen In tetrahydrofuran at 90℃; for 12h;
With hydrogen In tetrahydrofuran at 90℃; for 24h; 13 This example demonstrates the conversion of AMF to the saturated HMTF compound under hydrogen at high pressure. AMF (0.34 g, 2 mmol), THF (5 mL) and Pd/C (0.2 g) were charged to a high pressure reactor, which was pressurized to 1500 psi with H2. The reaction was stirred at 90° C. for 24 h. 1H and 13C NMR spectroscopy of the solution confirmed a quantitative conversion of AMF. HMTF was obtained as a major product.
  • 33
  • [ 10551-58-3 ]
  • [ 3238-40-2 ]
  • [ 90345-66-7 ]
YieldReaction ConditionsOperation in experiment
54% With oxygen; acetic acid at 100℃; for 2h; 15 OXIDATION OF AcHMF to FDCA Example 15[0052] A reaction mixture containing acetoxymethylfurfural (5.0 g), acetic acid (50 mL), cobalt acetate (0.13 g), manganese acetate (0.13 g), and sodium bromide (0.11 g) was placed in a 100 mL reactor and subjected to 500 psi oxygen at IOOC for 2 hours. The solid (2.53 g) was removed by filtration to give a 54% molar yield of FDCA from AcFIMF and a 5- (xcetoxymethyl)furan-2-carboxylic acid (AcMFCA) by-product.
  • 34
  • [ 470-23-5 ]
  • [ 823-82-5 ]
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
  • [ 7389-38-0 ]
YieldReaction ConditionsOperation in experiment
With Amberlist 15 resin; polymer-supported IBX amide reagent In dimethyl sulfoxide at 100℃; for 3h;
  • 35
  • [ 10551-58-3 ]
  • [ 7605-28-9 ]
  • [ 1352658-70-8 ]
YieldReaction ConditionsOperation in experiment
75% With sodium azide In water for 2h; Reflux; General procedure as exemplified for 5-p-Tolyl-2H-1,2,3-triazole-4-carbonitrile (7a). General procedure: A mixture of p-tolualdehyde (0.5 g, 4.2 mmol), phenylsulfonyl acetonitrile 6 (0.75 g, 4.2 mmol) and sodium azide (0.4 g, 6.25 mmol) in water (15 mL) was stirred under reflux for 1 h. The resulting mixture was then cooled to 5 °C, the solid obtained was filtered and washed with water (50 mL) to afford pure 7a (0.73 g, 95% yield) as a white crystals;
  • 36
  • [ 3484-35-3 ]
  • [ 10551-58-3 ]
  • [ 1332508-76-5 ]
  • 37
  • [ 10551-58-3 ]
  • [ 292638-85-8 ]
  • methyl 2-[hydroxy(5-(acetoxymethyl)-2-furanyl)methyl]acrylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With 1,4-diaza-bicyclo[2.2.2]octane In 1,4-dioxane; water at 20℃; Inert atmosphere; 4.2.2 General procedure for the formation of the Baylis-Hillman adducts 2a-f General procedure: Following the general procedure of Hu et al.,17 the aldehyde (30 mmol), acrylate (90 mmol), and DABCO (30 mmol, 3.36 g) were dissolved in 300 mL of 1,4-dioxane/water (1:1 v/v) and the mixture was stirred at room temperature overnight. After completion of the reaction, MTBE (500 mL) and H2O (250 mL) were added to the mixture. After phase separation, the organic layer was washed with brine (2 × 100 mL), dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. When required, the crude product was purified by column chromatography to yield the desired products 2a-f. The NMR spectra of 2a,27 2b,28 2c,29 and 2d28 corresponded to the published data.
  • 38
  • [ 67-47-0 ]
  • [ 141-78-6 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
90% With immobilized lipase B from Candida antarctica In neat (no solvent) at 20℃; for 24h; Enzymatic reaction;
With acyl transferase from Mycobacterium smegmatis In aq. phosphate buffer at 20℃; for 24h; Enzymatic reaction;
  • 39
  • [ 56278-50-3 ]
  • [ 10551-58-3 ]
  • [ 1630975-91-5 ]
YieldReaction ConditionsOperation in experiment
56% With tetrabutylammomium bromide; triethylamine In ethanol; water at 19℃; for 0.15h; Sonication; 2.2.2 Method B (US) General procedure: (a) Ultrasonic irradiation was performed using a ultransonic reactor (Elma transsonic 460, Elma, Singen, Germany), with a mechanical timer (60min with continuous hold) and heater switch, frequency of 35kHz using ethanol (10mL), and triethylamine (0.2mL). (b) US-PTC, TEA (0.2mL), 5mL of ethanol:H2O (50%), tetrabutylammonium bromide (TBAB) 20mol%, 35kHz. The solid products were collected by filtration and washed with ethanol:H2O (50%) to remove the TBAB and TEA to yield compounds 3.
  • 40
  • [ 10551-58-3 ]
  • (5-(hydroxymethyl)tetrahydrofuran-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With 5%-palladium/activated carbon; hydrogen In ethyl acetate at 60℃; for 1h; The multi-reactor system was used with a series of reactions using multifunctional catalyst systems comprising either 5% Pd/C or 10% Pd/C (0.1 g per g AcMF) in either EtOAc of 1,4-dioxane and AcMF with PuroliteTM D-5149 (0.3 g per g of AcMF), 7 bar hydrogen pressure and temperatures varied. The product selectivities were significantly affected by varying multifunctional catalyst systems, reaction times, and temperatures (Table 5). The highest selectivity of the fully reduced derivative of AcMF (7b) was 94% using 5% Pd/C with heating to 60°C for 1 hour. When the reaction was performed at ambient temperature for 2 hours, the selectivity of the fully reduced derivative decreased to 86% and the selectivity of 2-methyltetrahydrofuran (15) increased to 10%. As shown in Table5, entries 39 and 40, when the reaction was conducted under similar conditions employing either 5% or 10% Pd/C loading in either EtOAc or 1 ,4-dioxane, the fully reduced derivative (7b) was the primary product. The results from these experiments, in combination with results from examples 1-5, indicate that alkaline promoters increased the selectivity of the fully reduced derivatives.
With hydrogen at 100℃; for 10h; 4 Synthesis of 1,6-Hexanediol A parr reactor is loaded with the previous crude solution and Raney-Ni. The reactor is then flushed three times with nitrogen and subsequently with hydrogen. After flushing, the reactor is pressurized to 90 bar, and the reaction mixture is stirred and heated to 100 °C for 10 h. Product conversion and selectivity are analyzed by reverse phase HPLC. The crude reaction mixture is concentrated under vacuum.
With hydrogen at 100℃; for 10h; 4 A parr reactor is loaded with the previous crude solution and Raney-Ni. The reactor is then flushed three times with nitrogen and subsequently with hydrogen. After flushing, the reactor is pressurized to 90 bar, and the reaction mixture is stirred and heated to 100 °C for 10 h. Product conversion and selectivity are analyzed by reverse phase HPLC. The crude reaction mixture is concentrated under vacuum.
  • 41
  • [ 10551-58-3 ]
  • [ 96-47-9 ]
  • [ 1003-38-9 ]
  • [ 6126-49-4 ]
  • 2-(acetoxymethyl)-5-cyclohexyl-2-methyltetrahydrofuran [ No CAS ]
  • (5-(hydroxymethyl)tetrahydrofuran-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With palladium 10% on activated carbon; hydrogen In ethyl acetate for 2h; 35 Using the same apparatus and standard conditions as used in examples 1 - 32, a series of experiments was performed using a solution of AcMF furan starting material in solvent and catalyst systems. These studies were conducted to determine the effect of varying catalyst systems, reaction times and pressures, on AcMF conversion and furan derivative selectivity. An EtOAc solution of AcMF in the presence of a catalyst system was pressurized to 60 bar hydrogen and heated for 1 h. Results indicate the catalyst system comprising a combination of Pd/C and acid promoter trifluoracetic acid (Table 4, entry 33) gave a mixture of 46% fully reduced furan derivative (7b), 26% of 4b, 16% MTHF (15), and 5% DMTHF (6). The selectivity of DMTHF under the same conditions using the multifunctional catalyst system, Amberlyst 28, gave 48% higher selectivity as compared to the combined catalyst system. Increasing the reaction time to 2 h provided even higher selectivity of DMTHF at 63%. The multifunctional catalyst system of Amberlyst 10 at 14 bar hydrogen pressure, with heating to 60°C for 1 h, gave a 25% selectivity of the furan derivative MTHF, and partial conversion of AcMF. The results demonstrate the selectivity of furan derivatives was controlled by the choice of catalyst system, reaction temperature, and reaction time. Table 4. Furan derivative selectivity from AcMF using a combination of catalyst and acid promoter and multifunctional catalyst systems.
With palladium 10% on activated carbon; hydrogen; trifluoroacetic acid In ethyl acetate at 60℃; for 1h; 36 Using the same apparatus and standard conditions as used in examples 1 - 32, a series of experiments was performed using a solution of AcMF furan starting material in solvent and catalyst systems. These studies were conducted to determine the effect of varying catalyst systems, reaction times and pressures, on AcMF conversion and furan derivative selectivity. An EtOAc solution of AcMF in the presence of a catalyst system was pressurized to 60 bar hydrogen and heated for 1 h. Results indicate the catalyst system comprising a combination of Pd/C and acid promoter trifluoracetic acid (Table 4, entry 33) gave a mixture of 46% fully reduced furan derivative (7b), 26% of 4b, 16% MTHF (15), and 5% DMTHF (6). The selectivity of DMTHF under the same conditions using the multifunctional catalyst system, Amberlyst 28, gave 48% higher selectivity as compared to the combined catalyst system. Increasing the reaction time to 2 h provided even higher selectivity of DMTHF at 63%. The multifunctional catalyst system of Amberlyst 10 at 14 bar hydrogen pressure, with heating to 60°C for 1 h, gave a 25% selectivity of the furan derivative MTHF, and partial conversion of AcMF. The results demonstrate the selectivity of furan derivatives was controlled by the choice of catalyst system, reaction temperature, and reaction time. Table 4. Furan derivative selectivity from AcMF using a combination of catalyst and acid promoter and multifunctional catalyst systems.
  • 42
  • [ 10551-58-3 ]
  • [ 1003-38-9 ]
  • [ 6126-49-4 ]
  • 2-(acetoxymethyl)-5-cyclohexyl-2-methyltetrahydrofuran [ No CAS ]
  • (5-(hydroxymethyl)tetrahydrofuran-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With palladium 10% on activated carbon; hydrogen; trifluoroacetic acid In ethyl acetate for 1h; Using the same apparatus and standard conditions as used in examples 1 - 32, a series of experiments was performed using a solution of AcMF furan starting material in solvent and catalyst systems. These studies were conducted to determine the effect of varying catalyst systems, reaction times and pressures, on AcMF conversion and furan derivative selectivity. An EtOAc solution of AcMF in the presence of a catalyst system was pressurized to 60 bar hydrogen and heated for 1 h. Results indicate the catalyst system comprising a combination of Pd/C and acid promoter trifluoracetic acid (Table 4, entry 33) gave a mixture of 46% fully reduced furan derivative (7b), 26% of 4b, 16% MTHF (15), and 5% DMTHF (6). The selectivity of DMTHF under the same conditions using the multifunctional catalyst system, Amberlyst 28, gave 48% higher selectivity as compared to the combined catalyst system. Increasing the reaction time to 2 h provided even higher selectivity of DMTHF at 63%. The multifunctional catalyst system of Amberlyst 10 at 14 bar hydrogen pressure, with heating to 60°C for 1 h, gave a 25% selectivity of the furan derivative MTHF, and partial conversion of AcMF. The results demonstrate the selectivity of furan derivatives was controlled by the choice of catalyst system, reaction temperature, and reaction time. Table 4. Furan derivative selectivity from AcMF using a combination of catalyst and acid promoter and multifunctional catalyst systems.
  • 43
  • [ 10551-58-3 ]
  • [ 625-86-5 ]
  • 2-(acetoxymethyl)-5-cyclohexyl-2-methyltetrahydrofuran [ No CAS ]
  • (5-(hydroxymethyl)tetrahydrofuran-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With palladium 10% on activated carbon; hydrogen; trifluoroacetic acid for 1h; 33 Using the same apparatus and standard conditions as used in examples 1 - 32, a series of experiments was performed using a solution of AcMF furan starting material in solvent and catalyst systems. These studies were conducted to determine the effect of varying catalyst systems, reaction times and pressures, on AcMF conversion and furan derivative selectivity. An EtOAc solution of AcMF in the presence of a catalyst system was pressurized to 60 bar hydrogen and heated for 1 h. Results indicate the catalyst system comprising a combination of Pd/C and acid promoter trifluoracetic acid (Table 4, entry 33) gave a mixture of 46% fully reduced furan derivative (7b), 26% of 4b, 16% MTHF (15), and 5% DMTHF (6). The selectivity of DMTHF under the same conditions using the multifunctional catalyst system, Amberlyst 28, gave 48% higher selectivity as compared to the combined catalyst system. Increasing the reaction time to 2 h provided even higher selectivity of DMTHF at 63%. The multifunctional catalyst system of Amberlyst 10 at 14 bar hydrogen pressure, with heating to 60°C for 1 h, gave a 25% selectivity of the furan derivative MTHF, and partial conversion of AcMF. The results demonstrate the selectivity of furan derivatives was controlled by the choice of catalyst system, reaction temperature, and reaction time. Table 4. Furan derivative selectivity from AcMF using a combination of catalyst and acid promoter and multifunctional catalyst systems.
  • 44
  • [ 10551-58-3 ]
  • [ 1003-38-9 ]
  • 2-(acetoxymethyl)-5-cyclohexyl-2-methyltetrahydrofuran [ No CAS ]
  • (5-(hydroxymethyl)tetrahydrofuran-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With palladium 10% on activated carbon; hydrogen In 1,4-dioxane at 25℃; for 2h; The multi-reactor system was used with a series of reactions using multifunctional catalyst systems comprising either 5% Pd/C or 10% Pd/C (0.1 g per g AcMF) in either EtOAc of 1,4-dioxane and AcMF with PuroliteTM D-5149 (0.3 g per g of AcMF), 7 bar hydrogen pressure and temperatures varied. The product selectivities were significantly affected by varying multifunctional catalyst systems, reaction times, and temperatures (Table 5). The highest selectivity of the fully reduced derivative of AcMF (7b) was 94% using 5% Pd/C with heating to 60°C for 1 hour. When the reaction was performed at ambient temperature for 2 hours, the selectivity of the fully reduced derivative decreased to 86% and the selectivity of 2-methyltetrahydrofuran (15) increased to 10%. As shown in Table5, entries 39 and 40, when the reaction was conducted under similar conditions employing either 5% or 10% Pd/C loading in either EtOAc or 1 ,4-dioxane, the fully reduced derivative (7b) was the primary product. The results from these experiments, in combination with results from examples 1-5, indicate that alkaline promoters increased the selectivity of the fully reduced derivatives.
  • 45
  • [ 10551-58-3 ]
  • [ 625-86-5 ]
  • (5-(hydroxymethyl)tetrahydrofuran-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With 5%-palladium/activated carbon; hydrogen In ethyl acetate at 25℃; for 2h; The multi-reactor system was used with a series of reactions using multifunctional catalyst systems comprising either 5% Pd/C or 10% Pd/C (0.1 g per g AcMF) in either EtOAc of 1,4-dioxane and AcMF with PuroliteTM D-5149 (0.3 g per g of AcMF), 7 bar hydrogen pressure and temperatures varied. The product selectivities were significantly affected by varying multifunctional catalyst systems, reaction times, and temperatures (Table 5). The highest selectivity of the fully reduced derivative of AcMF (7b) was 94% using 5% Pd/C with heating to 60°C for 1 hour. When the reaction was performed at ambient temperature for 2 hours, the selectivity of the fully reduced derivative decreased to 86% and the selectivity of 2-methyltetrahydrofuran (15) increased to 10%. As shown in Table5, entries 39 and 40, when the reaction was conducted under similar conditions employing either 5% or 10% Pd/C loading in either EtOAc or 1 ,4-dioxane, the fully reduced derivative (7b) was the primary product. The results from these experiments, in combination with results from examples 1-5, indicate that alkaline promoters increased the selectivity of the fully reduced derivatives.
  • 46
  • [ 1623-88-7 ]
  • [ 10534-59-5 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
97% In acetonitrile at 20℃; for 0.0833333h; 1 Example 1 Example 1 In a round flask, 2 mL of methyl cyanide (acetonitrile) as an organic solvent was introduced, 0.145 g (1 mmol) of 5-chloromethylfurfural (CMF, compound I) was dissolved in the organic solvent, 0.302 g (1 mmol) of tetrabutylammonium acetate was added to the solution, and then the mixed solution was reacted at normal pressure and room temperature for 5 minutes. After the reaction, the reaction product was extracted by the addition of a small amount of water (5 mL) and ethyl acetate (added twice by 20 mL) to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure to obtain light yellow liquid 5-acetoxymethylfurfural (AcHMF, compound II). The yield thereof is 97%. It was ascertained by 1H-NMR that the light yellow liquid is a target material. Analysis data is as follows. AcHMF: 1H NMR (400 MHz, CDCl3) 9.65 (s, 1H), 7.25 (d, J=3.6, 1H), 6.62 (d, J=3.6, 1H), 5.13 (s, 2H), 2.12 (s, 3H)
96% In acetonitrile at 20℃;
  • 47
  • [ 1623-88-7 ]
  • [ 10581-12-1 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
95% In acetonitrile; at 20℃; under 760.051 Torr; for 0.0833333h; Example 2 In a round flask, 2 mL of methyl cyanide (acetonitrile) as an organic solvent was introduced, 0.145 g (1 mmol) of 5-chloromethylfurfural (CMF, compound I) was dissolved in the organic solvent, 0.133 g (1 mmol) of <strong>[10581-12-1]tetramethylammonium acetate</strong> was added to the solution, and then the mixed solution was reacted at normal pressure and room temperature for 5 minutes. After the reaction, the reaction product was extracted by the addition of a small amount of water (5 mL) and ethyl acetate (added twice by 20 mL) to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure to obtain light yellow liquid 5-acetoxymethylfurfural (AcHMF, compound II). The yield thereof is 95%. It was ascertained by 1H-NMR that the light yellow liquid is a target material. Analysis data is as follows. AcHMF: 1H NMR (400 MHz, CDCl3) 9.65 (s, 1H), 7.25 (d, J=3.6, 1H), 6.62 (d, J=3.6, 1H), 5.13 (s, 2H), 2.12 (s, 3H)
  • 48
  • [ 1623-88-7 ]
  • [ 143314-17-4 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
36% In acetonitrile; at 20℃; under 760.051 Torr; for 0.0833333h; Example 3 In a round flask, 2 mL of methyl cyanide (acetonitrile) as an organic solvent was introduced, 0.145 g (1 mmol) of 5-chloromethylfurfural (CMF, compound I) was dissolved in the organic solvent, 0.170 g (1 mmol) of <strong>[143314-17-4]1-ethyl-3-methylimidazolium acetate</strong> was added to the solution, and then the mixed solution was reacted at normal pressure and room temperature for 5 minutes. After the reaction, the reaction product was extracted by the addition of a small amount of water (5 mL) and ethyl acetate (added twice by 20 mL) to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure to obtain light yellow liquid 5-acetoxymethylfurfural (AcHMF, compound II). The yield thereof is 36%. It was ascertained by 1H-NMR that the light yellow liquid is a target material. Analysis data is as follows. AcHMF: 1H NMR (400 MHz, CDCl3) 9.65 (s, 1H), 7.25 (d, J=3.6, 1H), 6.62 (d, J=3.6, 1H), 5.13 (s, 2H), 2.12 (s, 3H)
  • 49
  • [ 10551-58-3 ]
  • [ 1883-75-6 ]
  • [ 6338-41-6 ]
  • 50
  • [ 1623-88-7 ]
  • [ 284049-75-8 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
37% In acetonitrile at 20℃; for 0.416667h;
  • 51
  • [ 10551-58-3 ]
  • [ 90345-66-7 ]
YieldReaction ConditionsOperation in experiment
91% With sodium chlorite; dihydrogen peroxide In water; acetonitrile 1.ii ii) Preparation of 5-acetyloxymethylfurancarboxylic acid (5): [R=CH3] ii) Preparation of 5-acetyloxymethylfurancarboxylic acid (5): [R=CH3]Into a 500 mL four necked round bottomed flask equipped with a mechanical stirrer, gas bubbler, thermometer socket are charged 5-acetyloxymethylfurfural (30 g) as obtained above and 300 mL acetonitrile. To the stirred solution, an aq. solution of sodium chlorite (24.2 g; 0.267 mol) and 50% hydrogen peroxide (25 mL; 0.367 mol) were added. After addition, the reaction mixture was stirred for 2-3 hours. The product was extracted with ethyl acetate. Excess solvent was recovered by distillation under reduced pressure to get 5-acetyloxymethylfurancarboxylic acid (29.9 g; 91 % by theory) as off-white solid. HPLC purity: > 98%
75% With sodium chlorite; sodium dihydrogenphosphate; dihydrogen peroxide In acetonitrile at 20℃; for 3h;
  • 52
  • [ 1623-88-7 ]
  • [ 127-09-3 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
97% With tetrabutylammonium acetate In acetonitrile at 40℃; for 12h; 1 0.145 g (1 mmol) of 5-chloromethyl furfural (CMF, compound I) was dissolved in acetonitrile as an organic solvent in a round flask and 0.060 g (0.2 mmol) of tetrabutylammonium acetate, And 0.271 g (3.3 mmol) of sodium acetate were placed and reacted at normal pressure and 40 ° C for 12 hours. After the reaction was completed, a small amount of water (5 ml) and ethyl acetate (20 ml each) were added and extracted. The obtained organic layer was concentrated under reduced pressure to obtain 5-acetoxymethyl furfural (AcHMF, compound II) in the form of a pale yellow liquid. The yield of the product was 97%.
Stage #1: sodium acetate With Amberlite IRA-900 In water for 1h; Stage #2: 5-chloromethylfurfural In acetonitrile at 50℃; for 12h;
In para-xylene Reflux; 4 Synthesis of 1,6-Hexanediol To a round bottom flask equipped with a stir bar and a condenser is added 5- chloromethylfurfural (CMF), sodium acetate (NaOAc) and p-xylene. The reaction mixture is heated to reflux until all NaCl is observed to crash out of the solution. The crude solution is then filtered and directly transferred in the parr reactor for next step.
In para-xylene Reflux; 4 To a round bottom flask equipped with a stir bar and a condenser is added 5-chloromethylfurfural (CMF), sodium acetate (NaOAc) and p-xylene. The reaction mixture is heated to reflux until all NaCl is observed to crash out of the solution. The crude solution is then filtered and directly transferred in the parr reactor for next step
Stage #1: 5-chloromethylfurfural With oxygen In acetonitrile Stage #2: sodium acetate With tetrabutyl-ammonium chloride In acetonitrile 1; 2 <Example 1: Oxidation reaction experiment> The reactor includes a reaction part, and two types of columns made of SUS material with a diameter of 20 cm and a height of 100 cm are connected. It was filled with 1.5 kg of Ru-MnCo2O4, which is a heterogeneous catalyst.Here, the Ru-MnCo2O4 was filled using the one prepared in Preparation Example 3. After charging, the reactor temperature was maintained in a vacuum at 150°C to remove adsorbed impurities.In the storage tank of the raw material aromatic heterocyclic compound, an aromatic heterocyclic compound (compound of formula 1, R1 = aldehyde, R2 = CH2Cl, corresponding to the material prepared in Preparation Example 1) at a concentration of 1 wt% is dissolved in acetonitrile as a polar solvent 5 liters were filled. After filling, it was pressurized to 3 bar with oxygen gas. At this time, since the pressurization pressure is proportional to the amount of oxygen dissolved in the aromatic heterocyclic compound, using a high pressure can improve the reaction rate.The raw material was supplied to the upper part of the column in a state of a solution pressurized in oxygen using a liquid mass feeder to the column of the previous stage, and the internal pressure of the column was adjusted in the range of 1-5 bar. The supplied aromatic heterocyclic compound solution flows to the bottom of the column by gravity, At this time, 15 g of tetrabutylammonium chloride (TBAC) as an onium-based compound and 10 g of NaOAc as an ion activator were added to the column of the previous stage.

  • 53
  • [ 10551-58-3 ]
  • [ 91-00-9 ]
  • N-(5-(acetoxymethyl)furfurylidene)-N-(diphenylmethyl)amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% In ethanol at 20℃; for 18h; Inert atmosphere; Preparation of Furfurylidene Imines General procedure: At r.t., benzhydrylamine (18.3 g, 100 mmol) was added to a solution of the aldehyde (100 mmol) in EtOH (400 mL) and the reaction mixture was stirred overnight. Product precipitation was observed in most cases and could be further promoted by cooling with an ice bath or by adding a few drops of water. The solids were filtered off, washed with cold Et2O and recrystallised from EtOH to yield analytically pure imines.
  • 54
  • [ 10551-58-3 ]
  • [ 100-61-8 ]
  • (5-(bis(4-(methylamino)phenyl)methyl)furan-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With ytterbium(III) triflate In acetonitrile at 40℃; for 28h; Inert atmosphere;
  • 55
  • [ 67-47-0 ]
  • [ 64-19-7 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
90% With tetrabutylammomium bromide; oxygen; sodium nitrite at 70℃; for 16h; Green chemistry;
With lipase In 2,2,4-trimethylpentane at 60℃; for 2h; Molecular sieve; Enzymatic reaction; 4.4.1. Synthesis of 5-Acetoxy Methyl Furfural (5-AMF) (1) A suspension of 5-HMF (23.8 mM) in 2,2,2-trimethylpentane (Isooctane) (0.1 L) wasrefluxed (200 rpm) with lipase (2.8 g), molecular sieves (5 g) and acetic acid (119 mM) for2 h at 60 C; yellow lipid; 1H-NMR (CDCl3): (ppm) 9.576 (s, 1H), 7.504 (d, J = 2.1 Hz, 1H),6.789 (d, J = 2.1 Hz, 1H), 5.131 (s, 2H), 2.077 (s, 3H); 13C-NMR: 178.3, 169.7, 155.2, 152.2,123.6, 112.9, 57.4, 20.4; MS: 168 [M]+; IR: 1742, 1678, 1271, 1223, 1023 cm1 (Figure 9).
  • 56
  • [ 1623-88-7 ]
  • C4H11NPol(1+)*C2H3O2(1-) [ No CAS ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
84% In acetonitrile at 50℃; for 24h; 1 The counter anion is acetate substituted with chloride in Amberite IRA-900 (macroreticular type, 650-820 , 1.0 meq. / Ml by wetted bed volumn) resin 4.8 mL of dichloromethane was then filtered and the swelling. After an organic solvent to the filtrate was added to the synthetic resin 4 ml acetonitrile (acetonitrile), and dissolved in 5-chloromethyl-furfural (CMF, Compound I) 0.173 g (1.2 mmol), was reacted for one day at normal pressure, 50 ° C. The mixture was filtered to give the, concentrated under reduced pressure to pale yellow liquid in the form of 5-acetoxy-methyl-furfural (AcHMF, compound II) were collected the reaction solution and washing liquid to the resin washed with acetonitrile. The yield of product was 84%.
  • 57
  • [ 57-48-7 ]
  • [ 64-19-7 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
73% With magnesium sulfate In 1,4-dioxane at 150℃; for 0.0166667h; Microwave irradiation; Green chemistry; 1 10 ml pressure vial to 0.120 g (0.666 mmol) of fructose and acetic acid 1 ml, 1 v / v% H 2 SO 4 in dioxane 0.357 ml (0.067 mmol), MgSO 4 0.020 g (0.133 mmol) were placed 150 , 200 It allowed to react for one minute at W. After the reaction was completed, which it was extracted by adding water (20 ml) and ethyl acetate (2 times by adding 30 ml). Concentrated under reduced pressure, the obtained organic layer to give the 5-acetoxy-methyl-furfural (AMF, Formula 3) of pale yellow solid. The yield of product was 73%
  • 58
  • [ 50-99-7 ]
  • [ 64-19-7 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
37% With sulfuric acid; magnesium sulfate In 1,4-dioxane at 150℃; for 0.0166667h; Microwave irradiation; Green chemistry; 7 10 ml pressure vial to 0.120 g (0.666 mmol) of glucose and acetic acid 1 ml, 1 v / v% H 2 SO 4 in dioxane 0.357 ml (0.067 mmol), MgSO 4 0.020 g (0.133 mmol) were placed 150 , 200 It allowed to react for one minute at W. After the reaction was completed, which it was extracted by adding water (20 ml) and ethyl acetate (2 times by adding 30 ml). Concentrated under reduced pressure, the obtained organic layer to give the 5-acetoxy-methyl-furfural (AMF, Formula 3) of pale yellow solid. The yield of product was 37%.
  • 59
  • D-fructose [ No CAS ]
  • [ 79-20-9 ]
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
1: 29.9 %Chromat. 2: 10.3 %Chromat. With lithium chloride at 200℃; for 16h; Autoclave; Inert atmosphere; 9 General procedure: In a first step (as an example of step (A-1 ) of a process according to the invention), a starting mixture was prepared by filling - 60 g of methyl acetate, - a specific amount of fructose (see experiments 1 to 12 in table 1 and experiments 21 to 24 in table 3 below) or an aqueous fructose syrup with at least 66.5 wt-% fructose and some glucose (see experiments 13 to 20 in table 2 below). and - a catalyst (also designated as "additive", only for experiments 9 to 13 and 15 to 20) into a steel autoclave reactor (inner volume 300 ml). The amounts of fructose or fructose syrup were in the range of from: Fructose: 3.0-12.0 g (see table 1 below); Fructose syrup: 6.0-38.0 g (see table 2 below). In a second step (as an example of step (A-2) of a process according to the invention), the filled steel autoclave reactor was tightly sealed and pressurized with nitrogen (total pressure 50 bar) and the reaction mixture inside the steel autoclave reactor was heated to a temperature of 100-240°C (see table 1 , 2 and 3 below) while stirring at 1000 rpm. After the corresponding reaction temperature was reached, the reaction temperature was maintained for 1-40 hours (see table 1 , 2 and 3 below) while continuing stirring the reaction mixture inside the heated and pressurized steel autoclave reactor. Subsequently, the steel autoclave reactor was (i) allowed to cool down to room temperature (approximately 22 °C), (ii) the pressure was released, and (iii) the steel autoclave reactor was opened. For further analysis, 1 imL of the resulting mixture comprising HMF, 5- (acetoxymethyl)furfural, acetic acid, methanol and a remaining fraction of the initially added 60 g of the MeOAc was subjected to GC analysis to quantify said reaction products.
1: 23.9 %Chromat. 2: 23 %Chromat. With sodium chloride at 220℃; for 2h; Autoclave; Inert atmosphere; 11 General procedure: In a first step (as an example of step (A-1 ) of a process according to the invention), a starting mixture was prepared by filling - 60 g of methyl acetate, - a specific amount of fructose (see experiments 1 to 12 in table 1 and experiments 21 to 24 in table 3 below) or an aqueous fructose syrup with at least 66.5 wt-% fructose and some glucose (see experiments 13 to 20 in table 2 below). and - a catalyst (also designated as "additive", only for experiments 9 to 13 and 15 to 20) into a steel autoclave reactor (inner volume 300 ml). The amounts of fructose or fructose syrup were in the range of from: Fructose: 3.0-12.0 g (see table 1 below); Fructose syrup: 6.0-38.0 g (see table 2 below). In a second step (as an example of step (A-2) of a process according to the invention), the filled steel autoclave reactor was tightly sealed and pressurized with nitrogen (total pressure 50 bar) and the reaction mixture inside the steel autoclave reactor was heated to a temperature of 100-240°C (see table 1 , 2 and 3 below) while stirring at 1000 rpm. After the corresponding reaction temperature was reached, the reaction temperature was maintained for 1-40 hours (see table 1 , 2 and 3 below) while continuing stirring the reaction mixture inside the heated and pressurized steel autoclave reactor. Subsequently, the steel autoclave reactor was (i) allowed to cool down to room temperature (approximately 22 °C), (ii) the pressure was released, and (iii) the steel autoclave reactor was opened. For further analysis, 1 imL of the resulting mixture comprising HMF, 5- (acetoxymethyl)furfural, acetic acid, methanol and a remaining fraction of the initially added 60 g of the MeOAc was subjected to GC analysis to quantify said reaction products.
  • 60
  • [ 57-48-7 ]
  • [ 79-20-9 ]
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
1: 29.9 %Chromat. 2: 10.3 %Chromat. With lithium chloride at 200℃; for 16h; Autoclave; Inert atmosphere; 9 Experiments 1 to 24: Reaction parameter screening Experimental procedure of screening experiments 1 to 24: Screening was carried out in a series of single experiments designated "Experiment 1 " to "Experiment 24". In each single experiment "1 " to "24", one or more carbohydrate compounds according to the present invention was at least partially converted into HMF and 5- (acetoxymethyl)furfural (as an example of a carboxylic acid ester of formula (I) according to the present invention) in methyl acetate (MeOAc, solvent used as an example of a carboxylic acid ester of formula (II) according to the present invention). The general experimental procedure for each screening experiment of "1 " to "24" was as follows: In a first step (as an example of step (A-1 ) of a process according to the invention), a starting mixture was prepared by filling - 60 g of methyl acetate, - a specific amount of fructose (see experiments 1 to 12 in table 1 and experiments 21 to 24 in table 3 below) or an agueous fructose syrup with at least 66.5 wt-% fructose and some glucose (see experiments 13 to 20 in table 2 below). and - a catalyst (also designated as "additive", only for experiments 9 to 13 and 15 to 20) into a steel autoclave reactor (inner volume 300 ml). The amounts of fructose or fructose syrup were in the range of from: Fructose: 3.0-12.0 g (see table 1 below); Fructose syrup: 6.0-38.0 g (see table 2 below). In a second step (as an example of step (A-2) of a process according to the invention), the filled steel autoclave reactor was tightly sealed and pressurized with nitrogen (total pressure 50 bar) and the reaction mixture inside the steel autoclave reactor was heated to a temperature of 100-240°C (see table 1 , 2 and 3 below) while stirring at 1000 rpm. After the corresponding reaction temperature was reached, the reaction temperature was maintained for 1-40 hours (see table 1 , 2 and 3 below) while continuing stirring the reaction mixture inside the heated and pressurized steel autoclave reactor. Subsequently, the steel autoclave reactor was (i) allowed to cool down to room temperature (approximately 22 °C), (ii) the pressure was released, and (iii) the steel autoclave reactor was opened. For further analysis, 1 mL of the resulting mixture comprising HMF, 5- (acetoxymethyl)furfural, acetic acid, methanol and a remaining fraction of the initially added 60 g of the MeOAc was subjected to GC analysis to quantify said reaction products.
1: 41.2 %Chromat. 2: 22.4 %Chromat. With sodium chloride In water at 220℃; for 2h; Autoclave; Inert atmosphere; 13 Experiments 1 to 24: Reaction parameter screening Experimental procedure of screening experiments 1 to 24: Screening was carried out in a series of single experiments designated "Experiment 1 " to "Experiment 24". In each single experiment "1 " to "24", one or more carbohydrate compounds according to the present invention was at least partially converted into HMF and 5- (acetoxymethyl)furfural (as an example of a carboxylic acid ester of formula (I) according to the present invention) in methyl acetate (MeOAc, solvent used as an example of a carboxylic acid ester of formula (II) according to the present invention). The general experimental procedure for each screening experiment of "1 " to "24" was as follows: In a first step (as an example of step (A-1 ) of a process according to the invention), a starting mixture was prepared by filling - 60 g of methyl acetate, - a specific amount of fructose (see experiments 1 to 12 in table 1 and experiments 21 to 24 in table 3 below) or an agueous fructose syrup with at least 66.5 wt-% fructose and some glucose (see experiments 13 to 20 in table 2 below). and - a catalyst (also designated as "additive", only for experiments 9 to 13 and 15 to 20) into a steel autoclave reactor (inner volume 300 ml). The amounts of fructose or fructose syrup were in the range of from: Fructose: 3.0-12.0 g (see table 1 below); Fructose syrup: 6.0-38.0 g (see table 2 below). In a second step (as an example of step (A-2) of a process according to the invention), the filled steel autoclave reactor was tightly sealed and pressurized with nitrogen (total pressure 50 bar) and the reaction mixture inside the steel autoclave reactor was heated to a temperature of 100-240°C (see table 1 , 2 and 3 below) while stirring at 1000 rpm. After the corresponding reaction temperature was reached, the reaction temperature was maintained for 1-40 hours (see table 1 , 2 and 3 below) while continuing stirring the reaction mixture inside the heated and pressurized steel autoclave reactor. Subsequently, the steel autoclave reactor was (i) allowed to cool down to room temperature (approximately 22 °C), (ii) the pressure was released, and (iii) the steel autoclave reactor was opened. For further analysis, 1 mL of the resulting mixture comprising HMF, 5- (acetoxymethyl)furfural, acetic acid, methanol and a remaining fraction of the initially added 60 g of the MeOAc was subjected to GC analysis to quantify said reaction products.
  • 61
  • [ 57-48-7 ]
  • [ 79-20-9 ]
  • [ 98-01-1 ]
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
1: 24.3 %Chromat. 2: 18.2 %Chromat. 3: 9.9 %Chromat. In water at 220℃; for 2h; Autoclave; Inert atmosphere; 14 Experiments 1 to 24: Reaction parameter screening Experimental procedure of screening experiments 1 to 24: Screening was carried out in a series of single experiments designated "Experiment 1 " to "Experiment 24". In each single experiment "1 " to "24", one or more carbohydrate compounds according to the present invention was at least partially converted into HMF and 5- (acetoxymethyl)furfural (as an example of a carboxylic acid ester of formula (I) according to the present invention) in methyl acetate (MeOAc, solvent used as an example of a carboxylic acid ester of formula (II) according to the present invention). The general experimental procedure for each screening experiment of "1 " to "24" was as follows: In a first step (as an example of step (A-1 ) of a process according to the invention), a starting mixture was prepared by filling - 60 g of methyl acetate, - a specific amount of fructose (see experiments 1 to 12 in table 1 and experiments 21 to 24 in table 3 below) or an agueous fructose syrup with at least 66.5 wt-% fructose and some glucose (see experiments 13 to 20 in table 2 below). and - a catalyst (also designated as "additive", only for experiments 9 to 13 and 15 to 20) into a steel autoclave reactor (inner volume 300 ml). The amounts of fructose or fructose syrup were in the range of from: Fructose: 3.0-12.0 g (see table 1 below); Fructose syrup: 6.0-38.0 g (see table 2 below). In a second step (as an example of step (A-2) of a process according to the invention), the filled steel autoclave reactor was tightly sealed and pressurized with nitrogen (total pressure 50 bar) and the reaction mixture inside the steel autoclave reactor was heated to a temperature of 100-240°C (see table 1 , 2 and 3 below) while stirring at 1000 rpm. After the corresponding reaction temperature was reached, the reaction temperature was maintained for 1-40 hours (see table 1 , 2 and 3 below) while continuing stirring the reaction mixture inside the heated and pressurized steel autoclave reactor. Subsequently, the steel autoclave reactor was (i) allowed to cool down to room temperature (approximately 22 °C), (ii) the pressure was released, and (iii) the steel autoclave reactor was opened. For further analysis, 1 mL of the resulting mixture comprising HMF, 5- (acetoxymethyl)furfural, acetic acid, methanol and a remaining fraction of the initially added 60 g of the MeOAc was subjected to GC analysis to quantify said reaction products.
1: 20.7 %Chromat. 2: 12.2 %Chromat. 3: 5.6 %Chromat. at 180℃; for 16h; Autoclave; Inert atmosphere; 5 Experiments 1 to 24: Reaction parameter screening Experimental procedure of screening experiments 1 to 24: Screening was carried out in a series of single experiments designated "Experiment 1 " to "Experiment 24". In each single experiment "1 " to "24", one or more carbohydrate compounds according to the present invention was at least partially converted into HMF and 5- (acetoxymethyl)furfural (as an example of a carboxylic acid ester of formula (I) according to the present invention) in methyl acetate (MeOAc, solvent used as an example of a carboxylic acid ester of formula (II) according to the present invention). The general experimental procedure for each screening experiment of "1 " to "24" was as follows: In a first step (as an example of step (A-1 ) of a process according to the invention), a starting mixture was prepared by filling - 60 g of methyl acetate, - a specific amount of fructose (see experiments 1 to 12 in table 1 and experiments 21 to 24 in table 3 below) or an agueous fructose syrup with at least 66.5 wt-% fructose and some glucose (see experiments 13 to 20 in table 2 below). and - a catalyst (also designated as "additive", only for experiments 9 to 13 and 15 to 20) into a steel autoclave reactor (inner volume 300 ml). The amounts of fructose or fructose syrup were in the range of from: Fructose: 3.0-12.0 g (see table 1 below); Fructose syrup: 6.0-38.0 g (see table 2 below). In a second step (as an example of step (A-2) of a process according to the invention), the filled steel autoclave reactor was tightly sealed and pressurized with nitrogen (total pressure 50 bar) and the reaction mixture inside the steel autoclave reactor was heated to a temperature of 100-240°C (see table 1 , 2 and 3 below) while stirring at 1000 rpm. After the corresponding reaction temperature was reached, the reaction temperature was maintained for 1-40 hours (see table 1 , 2 and 3 below) while continuing stirring the reaction mixture inside the heated and pressurized steel autoclave reactor. Subsequently, the steel autoclave reactor was (i) allowed to cool down to room temperature (approximately 22 °C), (ii) the pressure was released, and (iii) the steel autoclave reactor was opened. For further analysis, 1 mL of the resulting mixture comprising HMF, 5- (acetoxymethyl)furfural, acetic acid, methanol and a remaining fraction of the initially added 60 g of the MeOAc was subjected to GC analysis to quantify said reaction products.
  • 62
  • [ 10551-58-3 ]
  • [ 100-36-7 ]
  • (5-(((2-(diethylamino)ethyl)imino)methyl)furan-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% With magnesium sulfate In dichloromethane at 20℃; Inert atmosphere; Darkness;
  • 63
  • D-glucose pentaacetate [ No CAS ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
82% With sulfuric acid In acetic acid at 175℃; for 0.0833333h; Flow reactor;
  • 64
  • [ 534-22-5 ]
  • [ 10551-58-3 ]
  • [ 1309796-31-3 ]
YieldReaction ConditionsOperation in experiment
79% With 1-methyl-3-(4-sulfobutyl)-1H-imidazol-3-ium hydrogensulfate In water at 65℃; for 2h; Green chemistry;
  • 65
  • [ 10551-58-3 ]
  • [ 62-53-3 ]
  • C14H15NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With copper(I) iodide; phenylsilane In ethanol at 80℃; for 4h;
99 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; aniline In methanol at 25℃; for 3h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 80℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
  • 66
  • [ 10551-58-3 ]
  • 5-acetoxymethyl-α-hydroxyfuranmethanesulfonic acid sodium salt [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With sodium hydrogensulfite In ethanol; water; ethyl acetate at 40℃; for 16h; 5-Hydroxymethyl-α-hydroxyfuranmethanesulfonic Acid Sodium Salt (3a) General procedure: The synthesis of 3a is representative. To 5-hydroxymethylfurfural(200 mg, 1.6 mmol) and sodium bisulfite(148 mg, 1.6 mmol) was added 1.1 mL ethyl acetate,0.7 mL ethanol, and 0.2 mL of water. The solution wasbrought to 40 C and stirred for 16 h. After cooling to0 C, the solid precipitate was filtered and washed withethanol to afford 3a (275 mg, 75 %) as a white solid.
  • 67
  • [ 10551-58-3 ]
  • [ 4282-32-0 ]
  • 68
  • [ 10551-58-3 ]
  • [ 504-63-2 ]
  • C11H14O5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With indium(III) triflate; trimethyl orthoformate In dichloromethane at 20℃; 7 Synthesis of PD-HMF The HMF acetate obtained by the above method was dissolved in dichloromethane solution (HMF acetate concentration: 0.1 mol / L)a catalytic amount (0.01 equivalent) of indium trifluoromethanesulfonate (In (OTf)3) and an excess amount of trimethyl orthoformate and 1,3-propanediol were added thereto,the aldehyde moiety bound to the furan ring was converted to a cyclic acetal by stirring at room temperature. Finally, the product was reacted with sodium carbonate in a methanol solution to decompose the acetate site to obtain the objective propanediol-HMF acetal (PD-HMF).
With indium(III) triflate; trimethyl orthoformate In dichloromethane at 20℃; for 3h; 7 Synthesis of PD-HMF-Acetate To the dichloromethane solution in which the HMF acetate body obtained by the above method is dissolved(Concentration of HMF acetate: 0.1 mol / L),0.01 molar equivalent of In (OTf) 3 and an excess amount of trimethyl orthoformate and 1,3-propanediol were added to the HMF acetate form,The solution was stirred at room temperature for 3 hours.The catalyst was separated from the solution after the reaction,By further purifying by column chromatography,To obtain the objective PD-HMF-acetate.
With indium(III) triflate; trimethyl orthoformate In dichloromethane at 20℃; for 15h;
  • 69
  • [ 10551-58-3 ]
  • [ 107-21-1 ]
  • [ 126380-43-6 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 5-acetoxymethyl-2-furaldehyde; ethylene glycol With indium(III) triflate; trimethyl orthoformate In dichloromethane at 20℃; Stage #2: With methanol; sodium carbonate In dichloromethane 7 Synthesis of EG-HMF The HMF acetate obtained by the above method was dissolved in dichloromethane solution(Concentration of HMF acetate: 0.1 mol / L),A catalytic amount (0.01 equivalent)Of indium trifluoromethanesulfonate (In (OTf) 3)And an excess amount of trimethyl orthoformate and ethylene glycol were added,The aldehyde moiety bound to the furan ring was converted to a cyclic acetal by stirring at room temperature.Finally, the product is reacted with sodium carbonate in a methanol solution to decompose the acetate site,To obtain the objective ethylene glycol-HMF acetal (EG-HMF).
  • 70
  • [ 10551-58-3 ]
  • [ 504-63-2 ]
  • [5-(1,3-dioxan-2-yl)furan-2-yl]methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: 5-acetoxymethyl-2-furaldehyde; trimethyleneglycol With indium(III) triflate; trimethyl orthoformate In dichloromethane at 20℃; Stage #2: With methanol; sodium carbonate In dichloromethane 7 Synthesis of PD-HMF The HMF acetate obtained by the above method was dissolved in dichloromethane solution(Concentration of HMF acetate: 0.1 mol / L),A catalytic amount (0.01 equivalent) of indium trifluoromethane sulfonate(In (OTf) 3)And an excess amount of trimethyl orthoformate and 1,3-propanediol were added,The aldehyde moiety bound to the furan ring was converted to a cyclic acetal by stirring at room temperature.Finally, the product is reacted with sodium carbonate in a methanol solution to decompose the acetate site,To obtain the objective propanediol-HMF acetal (PD-HMF)
  • 71
  • [ 10551-58-3 ]
  • [ 108-24-7 ]
  • [ 54864-18-5 ]
YieldReaction ConditionsOperation in experiment
96% With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 0.5h; 4.4. Preparation of acylals 2 h-p. General Method B General procedure: Acetic acid anhydride (2mmol) and BF3-OEt2 (2 drops) were cooled down to 0°C. Aldehyde (1mmol) was added slowly with stirring, and the mixture was stirred at room temperature for 30min. The product mixture was poured into a 10% aqueous solution of NaOAc (20mL) and stirred rapidly for 10min. The product was extracted with ethyl ether (3×15mL), the extracts were combined, and washed with aqueous NaHCO3 followed by water. After drying over anhydrous sodium sulfate the crude product was concentrated under vacuum and isolated by recrystallization from ethyl ether/hexane or silica gel chromatography (ethyl acetate/hexane). (Furan-2-yl)methylene diacetate (2h): white crystals, 98% yield (194mg, 0.98mmol); 1H NMR (400MHz, CDCl3) δ 7.70 (s, 1H), 7.44 (dd, J=1.8, 0.8Hz, 1H), 6.52 (dd, J=3.3, 0.5Hz, 1H), 6.38 (dd, J=3.3, 1.8Hz, 1H), 2.12 (s, 6H); 13C NMR (100MHz, CDCl3) δ 168.36, 147.93, 143.62, 110.35, 109.67, 83.49, 20.64. 1H and 13C NMR data were in accordance with those reported in the literature [50].
  • 72
  • [ 54864-18-5 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
83% With bovine liver acetone powder In aq. phosphate buffer; acetone at 20℃; for 0.333333h; Enzymatic reaction; chemoselective reaction; 7 4.5. General deprotection protocol General procedure: A solution of diacetate 2 (1mmol) and BLAP (10mg) in phosphate buffer (50mM, pH 7.4) was stirred in a vortex (200rpm) at 20°C for for an appropriate time as required to complete the reaction. After complete conversion, as indicated by GC or TLC, the reaction mixture was extracted with ethyl acetate (3×15mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated in vacuum to give the corresponding aldehyde 1.
  • 73
  • [ 61-54-1 ]
  • [ 10551-58-3 ]
  • (5-(((2-(1H-indol-3-yl)ethyl)amino)methyl)furan-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
13.5% Stage #1: tryptamine; 5-acetoxymethyl-2-furaldehyde With acetic acid In methanol for 1h; Reflux; Stage #2: With methanol; sodium tetrahydroborate at 0℃; for 1h; Inert atmosphere; General procedure for the synthesis of amines via reductive amination General procedure: A mixture of primary amine (1.0 equi), aldehyde (1.1 equi) and acetic acid (3 drops) in MeOH (10 mL) was heated under reflux for 1 h. After cooling to RT, sodium borohydride (0.6 equi) was added and stirred at 0°C for 1 h under Argon. The saturated NaHCO3 was added and extracted with EtOAc (3×20 mL). The organic phase was dried (Na2SO4), filtered and concentrated to give the dark brown residue. The residue was purified by flash column chromatography.
  • 74
  • [ 10551-58-3 ]
  • [ 109-76-2 ]
  • (5-(((3-aminopropyl)amino)methyl)furan-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
63.6% Stage #1: 5-acetoxymethyl-2-furaldehyde; Trimethylenediamine With acetic acid In methanol for 1h; Reflux; Stage #2: With methanol; sodium tetrahydroborate at 0℃; for 1h; Inert atmosphere; General procedure for the synthesis of amines via reductive amination General procedure: A mixture of primary amine (1.0 equi), aldehyde (1.1 equi) and acetic acid (3 drops) in MeOH (10 mL) was heated under reflux for 1 h. After cooling to RT, sodium borohydride (0.6 equi) was added and stirred at 0°C for 1 h under Argon. The saturated NaHCO3 was added and extracted with EtOAc (3×20 mL). The organic phase was dried (Na2SO4), filtered and concentrated to give the dark brown residue. The residue was purified by flash column chromatography.
  • 75
  • 1,6-di-O-acetyl-D-fructofuranose [ No CAS ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
95.7% With sulfuric acid In dimethyl sulfoxide at 120℃; for 2h; Acidic conditions; 5-Acetoxymethyl-2-furfural (AMF) Dehydration of DAF into AMF was performed in organicsolvent using heterogeneous acid catalyst and a high temperature. Amberlyst 15, a type of cationexchange resin, was chosen as the acidic catalyst. Reaction conditions were: 50 mg DAF dissolved in5 mL solvent, 50 mg Amberlyst 15, stirring at 300 rpm, 120 °C for 8 h. After dehydration, Amberlyst 15was filtered out and the qualification and quantification of AMF in the reaction mixture was analyzedby HPLC and GC-MS (Figures S7 and S8). AMF was also isolated through vacuum distillation andanalyzed with 1H NMR (300 MHz, THF-d8): 9.62 (s, 1H on -CHO), 7.31-7.30 (d, 1H of C4 on furan ring),6.68-6.67 (d, 1H of C3 on furan ring), 5.13 (s, 2H of -CH2), 2.06 (s, 3H of -CH3) (Figure S4). 13C NMRof AMF (300 MHz, THF-d8): 176.91 (s, C in -CHO group), 169.23 (s, C in -COO- group), 155.57 (s, C2in the furan ring), 155.37 (s, C5 in the furan ring), 120.62 (s, C4 in the furan ring), 112.06 (s, C3 in thefuran ring), 57.27 (s, C in -CH2 group), 19.32 (s, C in -CH3 group) (Figure S5). GC-MS analysis with EIscan mode from -2.0 to +2.0 kV shows m/z: 282.2 (M - COCH3 + H+, 100%) (Figure S6).
  • 76
  • 1,6-di-O-acetyl-D-fructofuranose [ No CAS ]
  • [ 67-47-0 ]
  • [ 10551-58-3 ]
YieldReaction ConditionsOperation in experiment
1: 86.6% 2: 10.4% With sulfuric acid In dimethyl sulfoxide at 120℃; for 2h; Acidic conditions; 5-Acetoxymethyl-2-furfural (AMF) Dehydration of DAF into AMF was performed in organicsolvent using heterogeneous acid catalyst and a high temperature. Amberlyst 15, a type of cationexchange resin, was chosen as the acidic catalyst. Reaction conditions were: 50 mg DAF dissolved in5 mL solvent, 50 mg Amberlyst 15, stirring at 300 rpm, 120 °C for 8 h. After dehydration, Amberlyst 15was filtered out and the qualification and quantification of AMF in the reaction mixture was analyzedby HPLC and GC-MS (Figures S7 and S8). AMF was also isolated through vacuum distillation andanalyzed with 1H NMR (300 MHz, THF-d8): 9.62 (s, 1H on -CHO), 7.31-7.30 (d, 1H of C4 on furan ring),6.68-6.67 (d, 1H of C3 on furan ring), 5.13 (s, 2H of -CH2), 2.06 (s, 3H of -CH3) (Figure S4). 13C NMRof AMF (300 MHz, THF-d8): 176.91 (s, C in -CHO group), 169.23 (s, C in -COO- group), 155.57 (s, C2in the furan ring), 155.37 (s, C5 in the furan ring), 120.62 (s, C4 in the furan ring), 112.06 (s, C3 in thefuran ring), 57.27 (s, C in -CH2 group), 19.32 (s, C in -CH3 group) (Figure S5). GC-MS analysis with EIscan mode from -2.0 to +2.0 kV shows m/z: 282.2 (M - COCH3 + H+, 100%) (Figure S6).
  • 77
  • [ 10551-58-3 ]
  • furane-2,5-dicarboxylic acid disodium salt [ No CAS ]
YieldReaction ConditionsOperation in experiment
660g With 5% active carbon-supported ruthenium; water; sodium hydrogencarbonate at 130℃; for 4h; Autoclave; 1 Example 1 A basic aqueous solution composed of sodium hydrocarbonate (18 g) and deionized water (600 ml) was added into an autoclave. 5-acetoxymethylfurfural (6.7 g, 0.039 mole, 97% purity) and a wetted powdery oxidation catalyst (8.94 g, Ru/C (i.e., ruthenium carried on activated carbon), ruthenium content: 5 wt % based on 100 wt % of the oxidation catalyst, manufacturer: EVONIK, moisture content: 55.9%) were then added into the autoclave, followed by mixing the oxidation catalyst with the basic aqueous solution. Air was then introduced into the autoclave at a flow rate of 12 L/min, followed by an oxidation reaction at a temperature of 130° C. and a pressure of 20 kg/cm2 for 4 hours to form a reaction product. The temperature of the autoclave was reduced to room temperature (about 25° C.) and the pressure in the autoclave was released. The reaction product was then poured from the autoclave, followed by filtration of the reaction product with a filter paper to obtain a filter cake. The filter cake was rinsed with deionized water (50 ml) to obtain a light yellow filtrate containing sodium 2,5-furandicarboxylate (660 g).
  • 78
  • [ 10551-58-3 ]
  • [ 1883-75-6 ]
  • 2,5-bis(hydroxymethyl)furan monoacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium tetrahydroborate In methanol at 20℃; for 2h; Inert atmosphere; Overall yield = 26 percent; Overall yield = 0.528 g;
  • 79
  • [ 10551-58-3 ]
  • [ 108-24-7 ]
  • [ 5076-10-8 ]
YieldReaction ConditionsOperation in experiment
71% Stage #1: 5-acetoxymethyl-2-furaldehyde With sodium tetrahydroborate In methanol at 20℃; for 2h; Inert atmosphere; Stage #2: acetic anhydride With pyridine In acetonitrile at 20℃; for 16h; Cooling with ice; Inert atmosphere;
  • 80
  • [ 2033-24-1 ]
  • [ 10551-58-3 ]
  • 5-[5-[(acetyloxymethyl)-2-furanyl]methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% In water at 75℃; 4.1. General Synthesis Procedure General procedure: A mixture of Meldrum’s acid (6.9 mmol, 1 equiv, 1 g) and the corresponding conjugated aldehyde(6.9 mmol, 1 equiv) in deionized water (10 mL) was stirred at 75 °C for 2-4 h. Then, the precipitatewas filtered-o and dried to aord the targeted compounds. In case of no precipitate, the reactionmixture was extracted with ethyl acetate and the combined organic layers were dried over anhydrousmagnesium sulfate, filtered, and dried in vacuo.
  • 81
  • [ 10551-58-3 ]
  • [ 106-49-0 ]
  • C15H17NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
> 99 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; <i>p</i>-toluidine In methanol at 25℃; for 3h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 80℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
Multi-step reaction with 2 steps 1: methanol / 2 h / 25 °C 2: hydrogen; Pt/Al<SUB>2</SUB>O<SUB>3</SUB> / methanol / 25 °C / 3750.38 Torr / Flow reactor
  • 82
  • [ 10551-58-3 ]
  • [ 108-44-1 ]
  • C15H17NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
> 98 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; 1-amino-3-methylbenzene In methanol at 25℃; for 3h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 80℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
Multi-step reaction with 2 steps 1: methanol / 2 h / 25 °C 2: hydrogen; Pt/Al<SUB>2</SUB>O<SUB>3</SUB> / methanol / 25 °C / 3750.38 Torr / Flow reactor
  • 83
  • [ 10551-58-3 ]
  • [ 95-53-4 ]
  • C15H17NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
96 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; <i>o</i>-toluidine In methanol at 25℃; for 16h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 90℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
Multi-step reaction with 2 steps 1: methanol / 16 h / 25 °C 2: hydrogen; Pt/Al<SUB>2</SUB>O<SUB>3</SUB> / methanol / 35 °C / 3750.38 Torr / Flow reactor
  • 84
  • [ 10551-58-3 ]
  • [ 104-94-9 ]
  • C15H17NO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
99 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; 4-methoxy-aniline In methanol at 25℃; for 3h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 80℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
Multi-step reaction with 2 steps 1: methanol / 2 h / 25 °C 2: hydrogen; Pt/Al<SUB>2</SUB>O<SUB>3</SUB> / methanol / 25 °C / 3750.38 Torr / Flow reactor
  • 85
  • [ 10551-58-3 ]
  • [ 371-40-4 ]
  • C14H14FNO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
> 98 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; 4-fluoroaniline In methanol at 25℃; for 3h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 80℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
Multi-step reaction with 2 steps 1: methanol / 3 h / 25 °C 2: hydrogen; Pt/Al<SUB>2</SUB>O<SUB>3</SUB> / methanol / 35 °C / 3750.38 Torr / Flow reactor
  • 86
  • [ 10551-58-3 ]
  • [ 106-47-8 ]
  • C14H14ClNO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
97 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; 4-chloro-aniline In methanol at 25℃; for 3h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 80℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
Multi-step reaction with 2 steps 1: methanol / 3 h / 25 °C 2: hydrogen; Pt/Al<SUB>2</SUB>O<SUB>3</SUB> / methanol / 35 °C / 3750.38 Torr / Flow reactor
  • 87
  • [ 10551-58-3 ]
  • [ 108-42-9 ]
  • C12H21NO2 [ No CAS ]
  • C14H23NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
82 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; 3-chloro-aniline In methanol at 25℃; for 3h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 80℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
  • 88
  • [ 10551-58-3 ]
  • [ 111-26-2 ]
  • C14H14ClNO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
96 %Spectr. Stage #1: 5-acetoxymethyl-2-furaldehyde; hexan-1-amine In methanol at 25℃; for 16h; Stage #2: With (CuAl)O(x); hydrogen In methanol at 80℃; Flow reactor; 3.4. General Procedure for Reductive Amination of Furanic Aldehydes with Primary Amines General procedure: Depending on the nucleophilic properties of the amine, the solution of furanic aldehyde (0.05 M)and primary amine (0.05 M) in methanol was kept at 25 C for 3 or 16 h. Then, the reactionmixture was mixed with H2 and pumped through the flow reactor packed with the CuAlOx material.Catalytic experiments were performed in H-Cube Pro setup (Thalesnano, Budapest, Hungary) equippedwith a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [11,13]. Before the catalytic run,the catalyst (0.165 g of 250-500 m particles) was reduced by a mixture of hydrogen with methanol at120 C for 1 h (pressure of 10 bar, flow rates of methanol andH2 were 0.5 and 30 mL min1, respectively).Afterwards, the reaction mixture was pumped through the reactor instead of pure solvent, and thispoint in time was chosen as the starting point of the experiment.The reaction was carried out at temperature of 80-120 C, H2 pressure of 10 bar, liquid feed rate of0.5 mL min1 and hydrogen flow rate of 30 mL min1 (inlet H2/substrate molar ratio was 54). The useof a large excess of H2 in the reaction medium is necessary to avoid the influence of external masstransfer on the reaction progress [13]. The performance of the catalyst was evaluated by analysis of thesamples taken in the interval of 30-33 min from the beginning of the experiment. The composition ofthe reaction products was determined using 1H NMR spectroscopy in CDCl3. The error in determiningthe yield is 1%.
  • 89
  • [ 110-91-8 ]
  • [ 10551-58-3 ]
  • (5-(dimorpholinomethyl)furan-2-yl)methyl acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% With copper(II) bis(trifluoromethanesulfonate) In water at 20℃; for 0.0333333h;
  • 90
  • [ 10551-58-3 ]
  • [ 62-53-3 ]
  • C14H13NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
98 %Chromat. In methanol at 25℃; for 2h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 91
  • [ 10551-58-3 ]
  • [ 106-49-0 ]
  • C15H15NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 25℃; for 2h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 92
  • [ 10551-58-3 ]
  • [ 108-44-1 ]
  • C15H15NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 25℃; for 2h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 93
  • [ 10551-58-3 ]
  • [ 95-53-4 ]
  • C15H15NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 25℃; for 16h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 94
  • [ 10551-58-3 ]
  • [ 104-94-9 ]
  • C15H15NO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 25℃; for 2h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 95
  • [ 10551-58-3 ]
  • [ 371-40-4 ]
  • C14H12FNO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 25℃; for 3h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 96
  • [ 10551-58-3 ]
  • [ 106-47-8 ]
  • C14H12ClNO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 25℃; for 3h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 97
  • [ 10551-58-3 ]
  • [ 106-40-1 ]
  • C14H12BrNO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
5 %Spectr. In methanol at 25℃; for 3h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 98
  • [ 10551-58-3 ]
  • [ 540-37-4 ]
  • C14H12INO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 25℃; for 3h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 99
  • [ 10551-58-3 ]
  • [ 99-92-3 ]
  • C16H15NO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
18 %Spectr. In methanol at 25℃; for 16h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
  • 100
  • [ 10551-58-3 ]
  • [ 108-42-9 ]
  • C14H12ClNO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
6 %Spectr. In methanol at 25℃; for 3h; Catalysts performance General procedure: The solution of AMF (0.05 M) and primary amine (0.05 M) in methanol was kept at 25 °C for 2-16 h, depending on the nucleophilic properties of the amine. Afterwards, the reaction mixture was mixed with H2 and pumped through the flow reactor packed with the catalyst. Catalytic runs were carried out in H-Cube Pro setup (Thalesnano, Hungary) equipped with a 30 mm CatCart cartridge (CatCart30, 0.30 mL empty volume) [20,21,25]. In the case of Pt- and Pd-based samples, the catalyst (0.185 g) was preliminarily reduced with hydrogen dissolved in methanol at 70 °C for 15 min (H2 pressure of 5 bar, hydrogen flow rate of 30 mL min-1). The pure solvent was then changed to the reaction mixture and this point in time was chosen as the starting point of the experiment. The reaction was performed at temperature of 10-120 °C, H2 pressure of 5-10 bar, liquid feed rate of 0.5 mL min-1 and hydrogen flow rate of 30 mL min-1 (H2/AMF molar ratio was 54). The use of a high flow rate of H2 allows us to avoid the influence of external mass transfer in the course of the reaction [25]. The performance of the catalyst was evaluated by analysis of the samples taken in the interval of 30-33 min from the beginning of the experiment. The composition of the reaction products was determined using 1H NMR spectroscopy in CDCl3. The corresponding spectra and their interpretation are available in Supplementary Material. The error in determining the yield is ±1%.
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