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CAS No. : | 3458-28-4 | MDL No. : | MFCD00799233 |
Formula : | C6H12O6 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | - |
M.W : | 180.16 | Pubchem ID : | - |
Synonyms : |
Carubinose;NSC 26247;(+)-Mannose
|
Num. heavy atoms : | 12 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.83 |
Num. rotatable bonds : | 5 |
Num. H-bond acceptors : | 6.0 |
Num. H-bond donors : | 5.0 |
Molar Refractivity : | 36.97 |
TPSA : | 118.22 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -9.49 cm/s |
Log Po/w (iLOGP) : | -0.88 |
Log Po/w (XLOGP3) : | -2.94 |
Log Po/w (WLOGP) : | -3.38 |
Log Po/w (MLOGP) : | -2.91 |
Log Po/w (SILICOS-IT) : | -1.6 |
Consensus Log Po/w : | -2.34 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | 1.23 |
Solubility : | 3030.0 mg/ml ; 16.8 mol/l |
Class : | Highly soluble |
Log S (Ali) : | 1.02 |
Solubility : | 1870.0 mg/ml ; 10.4 mol/l |
Class : | Highly soluble |
Log S (SILICOS-IT) : | 2.45 |
Solubility : | 50500.0 mg/ml ; 281.0 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 3.31 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76.7% | With erbium(III) chloride In water at 240℃; for 0.5h; Inert atmosphere; Autoclave; | Reaction test and product analysis General procedure: All reactions were carried out in a 35 mL stainless steel autoclaveequipped with a mechanical stirrer. In a typical experiment, 0.1 gof substrate material, 0.05 g of catalyst and 30 mL of water wereadded to the reactor, after which the autoclave was purged threetimes with N2 and then pressurized to 2.0 MPa with N2 at roomtemperature. The reaction mixture was heated to 240 C unless otherwisestated and held at that temperature for 30 min with stirringat 600 rpm. After each reaction the reactor was quickly cooled toroom temperature using an ice/water mixture and then depressurized.The post-reaction sample was diluted with mobile phasesolution prior to analysis.Sample analyses were performed on a Shimadzu LC-20AT HPLCsystem equipped with a RID-10A detector and a Bio-Rad AminexHPX-87H ion exclusion column (300×7.8 mm), using 0.005 MH2SO4 as the mobile phase at a flow rate of 0.5 mL min-1. Thecolumn temperature was 50 C and the detector was set to 45 C.The amount of product was determined using calibration curvesgenerated with standard solutions. |
50% | With sodium hydroxide In water at 100℃; for 0.5h; Autoclave; Inert atmosphere; Green chemistry; chemoselective reaction; | |
With potassium hydroxide at 25℃; Einfluss der Alkali-Konzentration; |
With potassium hydroxide at 50℃; Einfluss der Alkali-Konzentration; | ||
With potassium hydroxide at 75℃; Einfluss der Alkali-Konzentration; | ||
With sodium hydroxide | ||
bei der Einw. von Bacillus bulgaricus; | ||
41 %Chromat. | Stage #1: D-Mannose With aluminum oxide; potassium hydroxide at 180℃; Microwave irradiation; Stage #2: With sulfuric acid In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With hydrogen In water at 120℃; for 1h; | 12 Example: 12 To 0.5 g of mannose in 40 ml of H20, HRO/Na-β catalyst (50 mg) was added in a reactor vessel. The reactor vessel was then heated at 120 °C for 1 h under H2 pressure (20 bar). After completion of the reaction, the catalyst was separated by using centrifuge and the obtained clear product mixture was analyzed by UHPLC. The reaction gave 100% conversion ofmannose with 100% yield of mannitol. |
78% | With sodium tetrahydroborate In water at 20℃; for 2h; | 4.5. Reduction of d-mannose to d-mannitol To a solution of d-mannose (1.0 g) in water (15 ml) was added an aqueous solution of sodium borohydride (0.2 g in 5 ml H2O). The reaction mixture was kept at room temperature for 2 h. When the reduction was complete the reaction mixture was acidified with a drop of acetic acid, deionized with cation/anion ion-exchange resin and evaporated to dryness. Crystallization from methanol afforded d-mannitol (780 mg; 78%). Mp 165-166 °C; [α]D = +23.7→+24.5 (c 10, Na2B4O7), 24 h, which was in accordance with the literature.r40 |
8.7% | With water; hydrogen at 99.84℃; for 0.5h; |
With platinum(IV) oxide; water Hydrogenation; | ||
With sodium amalgam | ||
With ammonium hydroxide; aluminium amalgam | ||
With ethanol; nickel | ||
With sodium borate; water | ||
With nickel; cyclohexanol at 120℃; Hydrogenation; | ||
With sodium tetrahydroborate In water for 3h; Ambient temperature; pH 10.5 (1M NaOH); | ||
With sodium tetrahydroborate at 4℃; for 2h; | ||
With sodium tetrahydroborate | ||
With monospecific xylose reductase from yeast Candida intermedia; NADPH In phosphate buffer at 25℃; | ||
With nickel(II) oxide-modified titania-supported ruthenium catalyst; hydrogen In water at 120℃; for 4h; Autoclave; | 2.3 Hydrogenation of d-mannose General procedure: 10 wt% d-mannose solution was prepared by dissolving 20 g of d-mannose in 180 ml de-ionized water. This solution was mixed with 1.0 g of catalyst Ru/(NiO-TiO2) to form the reaction slurry and thereafter the hydrogenation experiments of d-mannose were conducted in a 300 mL. The hydrogen gas was purged into the reactor at 2.0 MPa H2 pressure to deoxygenate the reaction mixture followed by stirring (400 rpm for 30 min) at room temperature and then pressure was released. The hydrogenation was initiated by stirring the reaction mixture at constant impeller speed of 1200 rpm and was continued for 240 min at temperature of 120 °C and hydrogen (H2) pressure of 40-55 bar. At the end of hydrogenation, the solution was cooled and the catalyst was allowed to settle at the bottom of reaction flask. The above mentioned procedure was followed with other catalyst Ru/TiO2 which was reduced at 320 °C [11,16]. The supernatant solution was filtered and then analyzed using a HPLC (Younglin Instrument, Acme 9000) equipped with refractive index (RI) detector and Sugar-Pak column. Deionized water was used as an eluent for the analysis at a flow rate of 0.4 mL/min at 70 °C. The temperature of RI detector was maintained at 35 °C throughout the analysis. | |
99 %Chromat. | With 5% nickel/activated carbon; hydrogen In ethanol; water at 80℃; for 12h; | |
Multi-step reaction with 2 steps 1.1: pyridine / 24 h / 0 - 23 °C 2.1: tris(pentafluorophenyl)borate / dichloromethane-d2 / 1 h / 23 °C / Inert atmosphere 2.2: Dowex® resin / 2 h 2.3: 0.5 h / 50 °C | ||
94.3 %Chromat. | With ruthenium-carbon composite; hydrogen In water at 160℃; for 1h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With potassium hydroxide; oxygen In water at 40℃; for 2h; | 7 In a 100-ml double jacketed reactor 0.91 g (5mmol) Mannose (1), 197 mg (0.02mmol Au) catalyst (3) followed by 30 ml water were added. The suspension was stirred at 600 RPM and heated to 4O0C (internal temperature) under oxygen gas (20 ml/min.) at atmospheric pressure for 2 hour. The rate of oxygen feed was controlled by a rotameter. The pH of the reaction mixture was continuously adjusted with a 2M potassium hydroxide solution (4) to pH 9.0. After cooling (15°C), the catalyst was separated by filtration and the cake rinsed with water. The analysis of the filtrate was performed with HPLC (BioRad Aminex HPX-87H, refractive index detector). The structure of 2 was confirmed by LC-MS (InertSil ODS 3, 210nm). ResultsWeight of filtrate: 41.27gGalactonic acid (2): 16%Galactose (1): n.f.Conversion of I: 100%Yield of 2: 91.0% |
With potassium hydroxide In water at 25℃; relative, initial rate; influence of var. catalysts; | ||
With sodium hydroxide; N-bromobenzenesulphonamide; sodium perchlorate; sodium In water at 30℃; Ea, ΔH(excit.), ΔG(excit.), ΔS(excit.); var concentration of reagents; |
With sodium hydroxide; tert-butylhypochlorite; sodium chloride In water at 24.9℃; var. of ratio, conc., pH, ionic strength, dielectric constant, temp., Ea, ΔH(excit.), ΔS(excit.), ΔG(excit.); | ||
With bromine | ||
With copper(II) hydroxide; sodium hydroxide | ||
With water; bromine; calcium carbonate Darstellung; | ||
With sodium hydroxide; platinum on activated charcoal; air at 22℃; | ||
With platinum(IV) oxide; air; water at 82 - 85℃; | ||
With methanol; potassium hypoiodite | ||
With water; bromine; barium carbonate | ||
durch Einw. von Penicillium luteum-purpurogenum; | ||
durch Einw. von Bacterium gluconicum; | ||
With calcium disulfite at 130℃; das Calciumsalz entsteht; | ||
durch Einw. von Aspergillus niger; | ||
95 %Spectr. | With dichloro-N-dimethylimidazolin-2-ylidene-(pentamethylcyclopentadienyl)iridium(III); sulfuric acid; water at 110℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With dimethylbromosulphonium bromide at 0 - 5℃; for 0.666667h; neat (no solvent); | |
70% | With hydrogenchloride In water at 20℃; for 1h; Inert atmosphere; | |
With hydrogenchloride |
With hydrogenchloride | ||
With hydrogenchloride at 0℃; | ||
With hydrogenchloride for 0.25h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid | ||
With hydrogenchloride | ||
With CuGGH metallopeptide based glycosidase; dihydrogen peroxide; sodium L-ascorbate In methanol; aq. phosphate buffer; water at 37℃; for 8h; Enzymatic reaction; | 1.2. Artificial glycosidase screening General procedure: CuGGH stock solution is prepared by titrating CuCl2 stock solution(1M) to GGH tripeptide solution (20 mM) till a final 1:1 ratio.The final concentration of CuGGH stock solution was diluted to5mM using deionized water. The formation of a CuGGH metallopeptidecomplex was confirmed by ESI-MS (m/z 166) and absorptionat 250 nm and 525 nm. The final 5mM CuGGH stocksolution should be purple in color.Mosquito HTS robotic liquid handling system (TTP Labtech Inc,Cambridge, MA) was programmed to mix freshly prepared sodiumascorbate solution (100 mM, 5 ml), freshly prepared hydrogenperoxide (100 mM, 5 ml), methyl glycoside stock solution (20 mM,5 ml), sodium phosphate buffer (pH 7.0, 250 mM, 5 ml) together withCuGGH stock solution (5 mM, 1 ml) together in 384-well plate. ForCuGGH single negative control: no CuGGH stock solution wasmixed in; For normal negative control: methyl glycoside stock solution(20 mM, 5 ml), sodium phosphate buffer (pH 7.0, 250 mM,5 ml) and 10 ml deionized water was mixed instead of catalyticcomponent. After 8 h incubation at 37 C, 80 ml 50/50 water/methanol solution was added into each sample well for a betterionization in ESI-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With camphor-10-sulfonic acid In dimethyl sulfoxide at 90℃; for 24h; | |
With camphor-10-sulfonic acid at 100℃; for 20h; | 8 4'-Pentenyl α-D-mannopyranose Camphorsulfonic acid (0.2 g) was added to stirred mixture of D-mannose (15 g) and 4-penten-1-ol (100 g) and the mixture heated to 100° C. After 20 hours the mixture was evaporated under reduced pressure and the residue chromatographed [SiO2, ethyl acetate] to give compound 8 (17.1 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67.8% | With aluminum tri-bromide In water; dimethyl sulfoxide at 130℃; for 0.5h; | 1-22 Implementation examples 1~15 General procedure: Using DMSO as the solvent, the total volume of the solvent is 1 mL, and 60 mg of mannose is added. AlCl3, CrCl3, MnCl2, NiCl2, FeCl2, FeCl3, CuCl2, LaCl3, CoCl2, ZnCl2, SnCl4, Al(CF3SO3)3, AlBr3 and inorganic acids H2SO4 and H3BO3 are catalysts, The catalyst was added in an amount of 10 mol% of mannose. React at 130 ° C for 30 min, After the reaction is completed, the reaction flask is placed in an ice water bath to cool. Dilute the appropriate amount of water into the reaction flask. Then adjust the dilution in the reaction flask to a constant volume. Finally, the content of 5-HMF in the diluted solution after constant volume was measured by an ultraviolet-visible spectrophotometer, and the yield of conversion of mannose to 5-HMF was calculated. |
61% | With chromium dichloride at 120℃; for 3h; Inert atmosphere; Ionic liquid; | Regiochemistry study. Regiochemistry of each hydroxyl group and the driving force of the formation of S, the different epimers of glucose have been studied.. Similar studies on epimers using CrCl2 were done by Binder, J. B. et al. with D-mannose, D- galactose, as well as other ketoses.36 However, in this study, only D-mannose (C-2 epimer of D-glucose) and D-galactose (C-4 epimer of D-glucose) were studied, with the addition of D- Allose (C-3 epimer of D-glucose) which was not previously done. The results are shown in Fig. 11 and in Table S8. |
41% | With Dowex 50Wx8-200 ion-exchange resin at 100℃; for 3h; Ionic liquid; Sealed tube; | General procedure: Dehydrations were performed using sealed tubes in concentrations of 10% (w/w) for both the carbohydrate and the heterogeneous catalyst, using 3 mL of [C4mim]Cl and keeping the temperature at 100 °C with continuous stirring for 3 hrs. |
26.9% | With Zr-salen-MCM-41 In dimethyl sulfoxide at 140℃; for 4h; Green chemistry; | 5 General procedure: (1) 100 mg of fructose was weighed and 50 mg of Zr-salen-MCM-41 catalyst was added to 25 mL of 2 mLDMS0The reactor was stirred in a 140 ° C oil bath for 1 to 5 h; (2) the reaction substrate fructose in (1) is replaced with any one of glucose, sucrose, inulin, galactose, mannose and cellulose, and the other conditions are not changed; (3) After the completion of the reaction is cooled, the solution is diluted with deionized water to 10 mL after 50 yL reaction, and the solution is determined by HPLC5-HMF yield. The results are shown in Table 2. Example 5 After the completion of the reaction, the solid acid catalyst used was separated by centrifugal precipitation,Rinse, dried and then put into the experimental case cycle. The yield of 5-HMF can be as high as 79.1% after four times of solid acid catalyst prepared by experimental data. Table 2 The yield of HMF produced by the reaction of the solid acid catalyst under different substrates |
10% | With SiO2-MgCl2 composite In acetonitrile at 140℃; for 24h; Autoclave; | |
With Phenylalanine In water at 98℃; for 10h; formation of furfural derivatives in amino-carbonyl reaction; various pH (2 - 12); | ||
0.264 mmol | With ytterbium(III) chloride In water at 140℃; for 1h; | |
With magnesium(II) chloride hexahydrate; 2-carboxyphenylboronic acid In N,N-dimethyl acetamide at 105℃; for 4h; | 2 example 2 10129] Table 2A lists results for the conversion of certain mono- and disaccharides (other than glucose and cellobiose) to HMF and thrfural. The pyranose sugars galactose and mannose and the furanose sugars sorbose and tagatose, were converted to HMF using the 2-substituted phenylboroic acid in the presence of magnesium ion and water in both a polar aprotic solvent other than an ionic liquid (e.g., DMA) and ionic liquid (e.g., [EMIM]C1.) Pentose sugars (xylose and arabinose) are converted under analogous reaction conditions to fiarthral. Table 28 lists results forthe conversion of fructose to HMF. Yields presented in Tables 2A and B are for unoptimized reaction conditions.10130] Tables 2C and 2D list results for the conversion of certain ketohexoses (including fructose) and certain aldohexoses (including glucose). Yields of 50% or more of HMF are observed from conversion of psicose, fructose, sorbose, glucose, mannose, gulose, idose, and galatose. Interestingly, there is a disparity in the reactivity of the different boronic acids with ketohexoses (see Table 2C). 2-Carboxyphenylbo- ronic acid attained its best HMF yields for all ketohexoses when it was used in conjunction with the magnesium salt. 2-Methoxycarbonylphenylboronic acid needed the salt forfructose and sorbose to achieve the best HMF yields, but did | |
With Aluminosilicate beta zeolite calcined at 750 °C In tetrahydrofuran; water; dimethyl sulfoxide at 180℃; for 3h; Autoclave; | ||
With 1-methylimidazole hydrogen sulfate In water; dimethyl sulfoxide at 180℃; for 6h; High pressure; Autoclave; | 2.3. Classical procedure for the catalytic conversion of GlcNAc into5-HMF General procedure: GlcNAc (100 mg, 0.452 mmol) was added into a mixed solvent composed of DMSO (8 g) and deionized water (12 g) in a 50 mL stainless steel vessel with a Teflon lining and sealed by a screw cap.Different amounts of ILs with different structures, used as catalysts,were loaded into the reactor. Then, the reactor was then immersed into a preheated oil bath, and the reaction mixture stirred for a given time. Time zero was recorded when the reactor was immersed in to the preheated oil bath. The clear solution darkened gradually overtime. After the scheduled time, the reactor was taken out from the oil bath and immediately submerged in an ice-water bath to quench the reaction. Then, the reaction mixture was taken out and filtered with filter paper to remove insoluble humin polymer. Afterwards,1mL of this reaction mixture was diluted with 5mL of methanol in a volumetric flask. This diluted solution was then taken out, filteredthrough a 0.22 mm PTFE filter, and injected into a glass tube. The 5-HMF yield was determined by high performance liquid chromatography(HPLC) of these aqueous solutions, using a standard curve(Fig. S1, Supplementary material) in order to quantify the amount. | |
33.7 %Chromat. | With Cr(salten) and 1-(1-vinylimidazol-3-ium-3-yl)propane-3-sulfonic acid sulfuric acid salt immobilized on MCM-41 In dimethyl sulfoxide at 140℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Stage #1: D-glucose With zirconium metal organic framework UiO-66 In propan-1-ol at 90℃; for 24h; Sealed tube; Stage #2: In water at 90℃; for 24h; | |
1: 34% 2: 10% | With SrO(SrTiO3)2 In water at 110℃; for 1h; | |
1: 25.97% 2: 6.95% | With 5% LaOH/C In water at 100℃; for 2h; Autoclave; Inert atmosphere; | 2 Isomerisation of Glucose into Fructose in the Presence of Various Solid Basic Catalysts at 100° C. The reaction of isomerisation of glucose into fructose is achieved in a 100 ml autoclave by applying a 2% by weight solution of glucose in water. The following amounts are introduced into the reactor: 30 g of distilled water, 0.6 g of glucose (2% by weight/water), 0.030 g of catalyst (5% by weight/glucose). No activation was applied to the solid catalysts. 20 bars of helium are introduced into the autoclave. The reaction medium is stirred by means of a magnetic stirrer. The reaction medium is brought to the reaction temperature by means of electric resistors regulated to 100° C. After 2 hours or 1 hour** of reaction at 100° C., the autoclave is cooled by means of an ice bath. The conversion of glucose and the fructose molar yield are determined by HPLC-RID analysis (column: COREGEL 87C). [0079] The isomerisation was achieved in the presence of various catalysts, i.e.: The isomerisation was achieved in the presence of various catalysts, i.e.: [0080] MgLaO (mixed oxide based on magnesium and lanthanum) (for 1 hour and 2 hours); [0081] LaO (simple lanthanum oxide/coal) (LaOH/C); [0082] ZrCs (comparative); [0083] hydrotalcite (Mg/Al=3) for 1 hour. (comparative) |
With (C12H25-O-C3H6-NH-CH2)2; nickel dichloride In methanol at 60℃; for 0.0833333h; other sugar, different ethylenediamine-derivatives; | ||
With potassium hydroxide In water at 25℃; for 336h; | ||
With Sn-zeolite-β In methanol; water at 110℃; for 0.5h; | ||
With paired tin-BEA zeolite for 2h; | 1 The benefit of creating the paired Lewis acid sites with directly adjacent sites in zeolite beta was illustrated by comparing the catalytic activity and selectivity of paired Sn-BEA and isolated Sn-BEA for the isomerization of sugars. Isomerization is known to be equilibrium limited to conversions around 50% with a competing side reaction of epimerization (FIG. 16A). The conversion of glucose for paired and isolated Sn-BEA was compared (FIG. 16B). Using the same tin content, paired Sn-BEA achieved 31% conversion in 2 hours (turnover frequency (TOF) of 0.70 min′) while isolated Sn-BEA only afforded 19% conversion (TOF of 0.39 min-1). The calculated TOF for paired Sn-BEA was most likely a lower bound for the actual value since the active site for paired Sn-BEA would include two tin atoms, resulting in a TOF of 1.4 min-1. Interestingly, paired Sn-BEA also achieved a greater selectivity for fructose (isomerization):mannose (epimerization) (4.5:1 at 50% conversion) than isolated tin (the range of 3.2-3.5:1 at 50% conversion. See FIG. 16C). For similar conversions, paired Sn-BEA achieved a higher fructose:mannose selectivity than any isolated Sn-BEA catalyst tested. Additionally, the increased selectivity appears to be a general phenomenon since the paired Sn-BEA achieved a higher selectivity than isolated Sn-BEA when converting xylose to xylulose (isomerization product)-paired Sn-BEA achieved a selectivity of 6.5:1 for xylulose:rabinose (epimerization product) compared to 6:1 for isolated Sn-BEA | |
1: 56 %Chromat. 2: 7.8 %Chromat. | With Sn-dealuminated beta zeolite In methanol at 110℃; for 1h; Inert atmosphere; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27% | With molybdic acid In water for 0.05h; microwave irradiation; | |
22.8% | With water at 160℃; for 0.5h; | |
7.9% | With triply sodium-exchanged zeolite tin-Beta In methanol at 79.84℃; for 0.5h; |
With (1R,2R)-N1,N2-diethylcyclohexane-1,2-diamine; nickel dichloride In methanol for 5h; Heating; other aldose; also (S,S)- and racemic (chxn)-deriv.; var. temp. and reaction times; epimerization equilibrium; | ||
With N,N,N,N,-tetramethylethylenediamine; nickel dichloride In methanol at 60℃; for 0.0833333h; C-2 epimerization; other metal chlorides and diamines; reaction with D-mannose; | ||
With phosphomolybdic acid In water at 100℃; for 1h; | ||
With LiNbMoO6 In water at 79.84℃; for 0.5h; | ||
With caesium modified hydrated phosphomolybdic acid supported on activated carbon In water at 59.84℃; for 0.5h; | ||
With sodium meta-tungstate at 230℃; for 0.00416667h; | 7 Example 7 (comparative) A solution of 1 wt% of glucose + 2500 ppm W (in the form of sodium metatungstate) was fed to the reactor and the glucose conversion was studied at 5, 10 and 15 seconds residence time at temperatures of 195 to 230 °C. Results are tabulated in Table 5. Formation of fructose was not observed in these experiments. Mannose was a major component formed in these experiments. Other identified products include erythrose, threose, glyceraldehyde, MPG and glycolaldehyde. It can be seen that glucose degradation in presence of tungsten results in the formation of mannose, rather than formation of fructose (Example 5 and 6) . Mannose is an epimer of glucose and can be converted in the hydrogenolysis reactor to MEG with the same efficiency as glucose (theoretical carbon selectivity of 100% to EG) . Glucose conversion/ degradation in presence of tungsten therefore results in a very high selectivity towards desired products. The selectively towards desired products is much higher than in absence of W (Example 5 and 6) . | |
With sodium vanadate; sulfuric acid; nitrogen In water at 100℃; | ||
With Rhodothermus marinus cellobiose 2-epimerase In aq. buffer at 70℃; for 24h; | ||
With tungsten(VI) oxide In methanol at 160℃; for 1h; Inert atmosphere; Autoclave; | ||
With phosphomolybdic acid In water at 85℃; for 1h; Autoclave; High pressure; | 2.3. Catalytic reaction General procedure: Hydrothermal reaction was performed in an autoclave reactor (BR-25, BERGHOF, Germany). In brief, required amounts of the substrate and catalyst were added into 7 mL of water and heated at the designatedtemperatures either in autogenous or aerobic condition. The reactionwas stopped by cooling down the reactor in an ice bath. Theremained cellulose was separated by filtration (ADVANTEC, 0.2 μm)and the filtrate was diluted with water before injected to HPLC. Thesamples were analyzed by using a Shimadzu Prominence HPLCequipped with a RID-10 A as well as a UV detector (210 nm) as describedin our previous study [32]. The yields of the products werecalculated based on carbon weight of the component and cellulose. Inthis context, carbon content of cellulose was determined by using anelemental analyzer (Vario EL cube elemental analyzer). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With camphorsulfonic acid In acetone at 20℃; | |
76% | With toluene-4-sulfonic acid In N,N-dimethyl-formamide at 20℃; Inert atmosphere; | |
73% | With toluene-4-sulfonic acid In acetone |
With toluene-4-sulfonic acid at 40℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.5% | With sulfuric acid; copper(II) sulfate | |
90% | With sulfuric acid for 4h; Ambient temperature; | |
85% | With sulfuric acid; copper(II) sulfate for 8h; | 3.2.1. 2,3;5,6-Di-O-isopropylidene--d-mannofuranose (7) Anhydrous CuSO4 (30 g, 188.6 mmol) was added in one portion to a suspension of d-mannose (20 g, 111.1 mmol) in dry acetone (200 mL); then sulfuric acid (6 drops) was added. The suspension was stirred for 8 h. The solution was filtered under vacuum and then stirred with potassium carbonate (3.4 g) at room temperature until (pH 8). The mixture was filtered through Celite and evaporation of solvent in vacuum gave a white solid, which was dissolved in CH2Cl2, and filtered through a bed of silica gel topped with Celite. Evaporation of solvent under reduced pressure gave a white solid. Recrystallisation from diethyl ether-hexane gave 7 as colorless crystals in (24.6 g 94.4 mmol) 85% yield. Mp 119-121 °C; [α]D +12.1 (c 1.1, CHCl3); IR: νmax (KBr) 3441 cm-1 (OH); 1H NMR (200 MHz, CDCl3): δ 1.3 (s, 3H), 1.32 (s, 3H), 1.35 (s, 3H), 1.4 (s, 3H), 3.0 (br s, 1H, OH), 4.0 (dd, 1H, J = 5.1, 8.6 Hz, H-6), 4.1 (dd, 1H, J = 6.0, 8.6 Hz, H-61), 4.15 (dd, 1H, J = 3.7, 7.2 Hz, H-4), 4.3-4.4 (m, 1H, H-5), 4.6 (d, 1H, J = 5.9 Hz, H-2), 4.8 (dd, 1H, J = 3.7, 5.9 Hz, H-3), 5.31 (br s, 1H, H-1); FABMS: 261 (M+1)+; Anal. Calcd for C12H20O6: C, 55.37; H, 7.74. Found: C, 55.33; H, 7.71. |
82% | With sulfuric acid In water | |
With hydrogen cation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With toluene-4-sulfonic acid for 28h; Reflux; | |
85% | With iodine for 0.333333h; Heating; | |
85% | Stage #1: D-Mannose; acetone With iodine at 20℃; for 18h; Stage #2: With sodium thiosulfate In water Stage #3: With sodium hydrogencarbonate In water | Mannose protection: preparation of r2,3,5,61-di-O-isopropylidene-D-MannoseIn a three-necked flask were introduced 50.8 g of D-mannose (0.282 mol), 2.5 L of acetone and 14.3 g of iodine sublimate (56.4 mmol, 0.2 eq.). The medium was stirred at room temperature until solubilization of mannose was complete (about 18h). 640 ml of a 10% sodium thiosulfate aqueous solution were added. The pH value was brought back near to neutrality with a sodium hydrogenocarbonate saturated solution. After addition of the sodium chloride saturated solution, the organic phase was collected and extracted with chloroform. The combined organic phases were then dried on magnesium sulfate, filtered, and then evaporated. A yellow solid was produced, that was recristallized in a hexane/acetone mixture (80/20).-2) g) 3.2 1H NMR (400.13 MHz, CDCI3): ? 1 .34 (s, 3H, CH3), 1 .39 (s, 3H, CH3), 1 .47 (s, 3H, CH3),1 .48 (s, 3H, CH3), 3.45 (d, 1 H, 3JH-H = 2.4 Hz, OH), 4.08 (dd, 2H, 2JH-H = 5.5 Hz, 3JH-H = 1 .0 Hz, 6CH2), 4.19 (dd, 1 H, 3JH-H = 7.0 Hz, 3JH-H = 3.7 Hz, 4CH), 4.41 (q broad, 1 H, 3JH-H = 5.5 Hz, 5CH), 4.62 (d, 1 H, 3JN-H = 5.9 Hz, 2CH), 4.82 (dd, 2H, 3JH-H = 5.9 Hz, 3JH-H = 3.7 Hz, 3CH), 5.39 (d, 1 H, |
82% | With phosphorus pentoxide for 12h; Inert atmosphere; | |
78% | With sulfuric acid; iodine for 6h; Reflux; | |
75% | With sulfuric acid at 20℃; for 4h; Inert atmosphere; | 1 4.1.1 2,3:5,6-Di-O-isopropylidene-α-d-mannofuranose (1) Concd sulfuric acid (14 ml) was added to a solution of d-mannose (20 g, 0.11 mol) in anhydrous acetone (30 ml) and the mixture was stirred at rt for 4 h then neutralized with satd Na2CO3 solution. The reaction mixture was filtered and the filtrate was extracted using ethyl acetate (3 * 100 ml). The organic layers were evaporated and concentrated to dryness under reduced pressure gave 1 (21.6 g, 75%) as white crystals mp 121-122 °C. 1H NMR (300 MHz, CDCl3 δ 1.31 (s, 3H, CH3), 1.36 (s, 3H, CH3), 1.44 (s, 3H, CH3), 1.45 (s, 3H, CH3), 2.90 (br s, 1H), 4.05 (m, 2H), 4.16 (dd, J = 3.6, 7.1 Hz, 1H), 4.39 (ddd, J = 5.4, 5.5, 7.1 Hz, 1H), 4.59 (d, J = 5.9 Hz, 1H), 4.79 (dd, J = 3.6, 5.9 Hz, 1H), 5.36 (d, J = 3.6 Hz, 1H). |
67% | Stage #1: D-Mannose; acetone With sulfuric acid at 20℃; for 12h; Stage #2: With sodium carbonate; pyrographite for 1h; Heating; | |
51% | With iodine at 20℃; for 2h; | 1 4.2.1. (3aS,4S,6R,6aS)-6-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-ol (5) Iodine (1.42 g, 5.6 mmol) was added to a suspension of d-mannose (5.0 g, 27.8 mmol) in acetone (250 mL) and the mixture was stirred for 2 h at ambient temperature. Then the reaction mixture was cooled down to 0 °C quenched with aqueous sodium bicarbonate and sodium thiosulfate. The mixture was extracted with CH2Cl2 (3×). The combined organic layers were dried (Na2SO4), filtered, and the solvent was removed in vacuo. The crude product was crystallized from an acetone/n-hexane mixture to give 5 as colorless solid (3.66 g, 14.1 mmol, 51%). Mp: 125 °C; +16.1 (8.1; CH2Cl2); 1H NMR (CDCl3): δ (ppm) = 1.32 (s, 3H, CH3), 1.38 (s, 3H, CH3), 1.45 (s, 3H, CH3), 1.46 (s, 3H, CH3), 2.92 (d, J = 2.4 Hz, OH), 4.02-4.11 (m, 2H, OCHCH2O), 4.18 (dd, J = 7.2/3.7 Hz, 1H, 6-H), 4.37-4.43 (m, 1H, OCHCH2O), 4.62 (d, J = 5.9 Hz, 1H, 3a-H), 4.81 (dd, J = 5.9/3.7 Hz, 1H, 6a-H), 5.38 (d, J = 2.4 Hz, 4-H); 13C NMR (CDCl3): δ (ppm) = 24.5 (1C, C(CH3)2), 25.3 (1C, C(CH3)2), 25.9 (1C, C(CH3)2), 27.1 (1C, C(CH3)2), 66.7 (1C, OCHCH2O), 73.4 (1C, OCHCH2O), 79.7 (1C, C-6a), 80.3 (1C, C-6), 85.5 (1C, C-3a), 101.3 (1C, C-4), 109.2 (1C, C(CH3)2), 112.8 (1C, C(CH3)2); IR (neat): ν (cm-1) = 3436, 2978, 2948, 2899, 1372, 1201, 1060, 975, 838; HRMS (m/z): [M+Na]+ calcd for C12H20O6Na, 283.1152; found, 283.1152. |
With sulfuric acid In water at 20℃; for 1h; | ||
With iodine at 20℃; for 2h; | ||
With sulfuric acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 60% 2: 25% 3: 14% | With ammonium cerium(IV) nitrate In N,N-dimethyl-formamide at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With pyridine at 20℃; for 4h; Inert atmosphere; | General procedure for the preparation of 1,5-anhydroalditol (1 mmol scale) General procedure: To a stirred solution of unprotected carbohydrate (1 mmol) in dry pyridine (5 ml), trimethylsilyl chloride (1.1 equiv against a hydroxyl group) was slowly added at rt under Ar atmosphere and the reaction mixture was stirred for 4 h at rt. n-Hexane (50 ml) and crushed ice (10 mL) were added to the reaction mixture successively, and the organic layer was extracted with iced water (10 mL×3), dried over Na2SO4, and evaporated in vacuo to afford per-O-TMS-glycoside as an oil in quantitative yield. To a solution of the per-O-TMS-glycoside (1 mmol) in dry CH2Cl2 (3 mL), trimethylsilyl iodide (140 μL, 1mmol) was added at rt under Ar atmosphere and the reaction mixture was stirred for 0.5 h. Then, 3 mol LiBH4 solution (670 μL, 2 mmol) in THF was added to the reaction mixture, and stirred for another 4 h at rt. n-Hexane (30 ml) and crushed ice (10 mL) were slowly added to the reaction mixture successively, and the organic layer was extracted with iced water (10 mL×5) to neutralize, dried over Na2SO4, and evaporated in vacuo to afford crude product as an oil. To remove the TMS groups, the crude product was treated with acidic resin (Dowex 50W, H+ form) in MeOH (15 mL), the reaction could be monitored by TLC, and the reaction was normally finished within 1 h. After filtration of the resin and concentration, the residue was purified by silica gel column chromatography (CHCl3/MeOH=20:1-4:1) to afford final product as white powder. Compound 1 (1,5-anhydro-D-glucitol, 1,5-AG): mp 139-140 °C; [α]D +38.9 (c 1.0, H2O); 1H NMR (600 MHz, D2O, δ) 3.78 (1H, dd, J=5.5, 11.0 Hz), 3.68 (1H, br d, J=11.5 Hz), 3.48 (1H, br dd, J=4.5, 11.5 Hz), 3.39 (1H, m), 3.24 (1H, m), 3.15 (2H, m), 3.08 (1H, t, J=11.0 Hz); 13C NMR (125 MHz, D2O, δ), 81.1, 78.3, 70.5, 70.2, 69.6, 61.7; HRESIMS m/z 187.0581 [M+Na]+ (calcd for C6H12O5Na, 187.0582). Compound 2 (1,5-anhydro-D-galactitol): mp 125-126 °C; [α]D+78.7 (c 1.0, H2O); 1H NMR (600 MHz, D2O, δ) 3.80 (1H, dd, J=5.5, 11.0 Hz), 3.76 (1H, d, J=3.5 Hz), 3.64 (1H, ddd, J=5.5, 10.0, 10.0 Hz), 3.55-3.48 (2H, m), 3.38 (2H, m), 3.00 (1H, t, J=11.0 Hz); 13C NMR (125 MHz, D2O, δ) 80.2, 74.9, 70.0, 69.9, 67.5, 62.2; HRESIMS m/z 187.0580 [M+Na]+ (calcd for C6H12O5Na, 187.0582). Compound 3 (1,5-anhydro-D-mannitol): mp 153-155 °C; [α]D -48.2 (c 1.0, H2O); 1H NMR (600 MHz, D2O, δ) 3.79 (1H, br t, J=~0.5 Hz), 3.74 (1H, dd, J=2.0, 12.5 Hz), 3.70 (1H, dd, J=2.5, 12.5 Hz), 3.50 (1H, dd, J=7.0, 12.5 Hz), 3.45 (2H, m), 3.40 (1H, t, J=9.5 Hz), 3.11 (1H, ddd, J=2.5, 7.0, 9.5 Hz); 13C NMR (125 MHz, D2O, δ) 81.3, 74.3, 70.6, 69.9, 68.1, 62.0; HRESIMS m/z 187.0582 [M+Na]+ (calcd for C6H12O5Na, 187.0582). Compound 4 (1,5-anhydro-L-rhamnitol): mp 120-122 °C; [α]D +82.8 (c 1.0, H2O); 1H NMR (600 MHz, CD3OD, δ) 3.84-3.82 (2H, m), 3.52 (1H, br d, J=13.0 Hz), 3.41 (1H, dd, J=3.5, 9.5 Hz), 3.34-3.30 (1H, overlapped with solvent), 3.14 (1H, dq, J=6.0, 9.5 Hz), 1.26 (3H, d, J=6.0 Hz); 13C NMR (125 MHz, CD3OD, δ) 78.9, 76.4, 75.1, 72.1, 71.8, 19.1; HRESIMS m/z 171.0632 [M+Na]+ (calcd for C6H12O4Na, 171.0633). Compound 5 (1,5-anhydro-L-fucitol): mp 118-120 °C; [α]D -62.4 (c 1.0, MeOH); 1H NMR (600 MHz, CD3OD, δ) 3.84 (1H, dd, J=5.5, 11.0 Hz), 3.74 (1H, m), 3.62 (1H, br d, J=3.5 Hz), 3.50 (1H, br q, J=6.5 Hz), 3.37 (1H, dd, J=3.5, 9.5 Hz), 3.07 (1H, t, J=11.0 Hz), 1.21 (3H, d, J=6.5 Hz); 13C NMR (125 MHz, CD3OD, δ) 77.5, 77.3, 74.3, 72.0, 69.0, 17.9; HRESIMS m/z 171.0631 [M+Na]+ (calcd for C6H12O4Na, 171.0633). Compound 6 (1,5-anhydroxylitol): mp 86-89 °C; 1H NMR (600 MHz, D2O, δ) 3.75 (2H, dd, J=5.0, 11.0 Hz), 3.38 (2H, m), 3.20 (1H, t, J=9.5 Hz), 3.03 (2H, t, J=11.0 Hz); 13C NMR (125 MHz, D2O, δ) 78.0, 70.3, 70.2; HRESIMS m/z 157.0476 [M+Na]+ (calcd for C5H10O4Na, 157.0477). |
With pyridine; 1,1,1,3,3,3-hexamethyl-disilazane at 20℃; for 0.583333h; | ||
With triethylamine In N,N-dimethyl-formamide at 0 - 25℃; Inert atmosphere; | 32.3 Step 3: PerTrimethylsilane-D-mannose In a 200mL round bottom flask, D-mannose (20g, 111mmol, 1.0eq) was dissolved in DMF (25mL). To above solution was added TEA (80mL, 577mmol, 5.2eq). The solution was cooled to 0°C. To above solution was added TMS-Cl (73.8mL, 577mmol, 5.2eq) dropwise. The mixture was warmed to 25°C and stirred at this temperature for 4h. The mixture was poured into ice/hexanes (1/1, 100mL), extracted with hexanes (50ml x3), washed with water (20mL x3). The organics were dried over MgSO4, filtered and concentrated to give the title compound. 1H NMR (in CDCl3, 500MHz): 4.89 (1H, H1, d, J=2.1Hz), 3.5-3.9 (m, 6H, H2-H6), 0.1(m, 45H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With hydrogen In methanol; water at 40℃; for 4.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With toluene-4-sulfonic acid In acetone at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With pyridine at 0 - 20℃; | |
89% | With iodine for 2h; cooling; | |
63% | With potassium acetate at 90℃; for 4h; | 34.1 (1) Preparation of 1,2,3,4,6-O-pentaacetyl-D-mannose Add mannose (4.5g) at room temperatureAnd potassium acetate (4.9g) dissolved in acetic anhydride (25mL),It was then stirred at 90 ° C for 4h.After the reaction was completed, the room temperature was returned, and the solvent was removed by an oil pump.100 mL of ethyl acetate was added to the reaction solution, followed by washing with a saturated aqueous sodium hydrogen carbonate solution, the aqueous phase was extracted with ethyl acetate, and the organic phases were combined.The organic phase was washed successively with a saturated aqueous sodium hydrogen carbonate solution, distilled water, and a saturated sodium chloride solution.It was then dried over anhydrous sodium sulfate and recrystallized with ethanol.6.3 g of product was obtained with a yield of 63%. |
With pyridine | ||
With pyridine | ||
With perchloric acid In water at 0℃; for 1h; | ||
With perchloric acid | ||
With perchloric acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 62% 2: 22% | In pyridine at 22℃; for 48h; | To a stirred mixture of D-mannose (0.76 g, 4.2 mmol) in pyridine (4.0 mL) and butyric anhydride (4.0 mL, 24.5 mmol) at 22 0C was added DMAP (cat.). After 48 h, the reaction mixture was co-concentrated with toluene (3 x 10 mL). The residue was dissolved in CH2Cl2 (100 mL), washed with dilute HCl (100 mL), water (100 mL) and saturated aqueous NaHCO3 (100 mL). The organic layer was dried (Na2SO4), filtered and concentrated. Column chromatography (ethyl acetate-hexanes) of the residue gave pure α- (1.4 g, 62 %) and β- (0.5 g, 22 %) anomers of 1 as oil.1,2,3,4,6-Penta-O-butanoyl-α-D-mannopyranose (α-ButsMannose): NMR (CDCl3) 1H-NMR (400 MHz): δ 6.08 (d, IH, J= 2.0), 5.38 (t, IH, J= 10.2), 5.34 (dd, IH, J= 10.1, J= 3.4), 5.27 (dd, IH, J = 2.9, J= 2.0), 4.21 (dd, IH, J = 12.4, J = 5.0), 4.12 (dd, IH, J = 12.4, J = 2.1), 4.02 (ddd, IH, J = 9.2, J = 4.9, J = 2.1), 2.41-2.17 (m, 10H), 1.74-1.52 (m, 10H), 1.00-0.87 (m, 15H); 13C-NMR (IOO MHz): δ 173.1, 172.5, 172.2, 172.0, 170.7, 90.4 (1Jc-H = 177), 70.8, 68.7, 68.1, 65.1, 61.8, 35.9 (4C), 35.8, 18.4, 18.3, 18.2 (2C), 18.2, 13.6, 13.5 (4C); MALDI-MS (m/z): [M + Na]+ calcd for C26H42NaO11, 553.2619; found, 553.2326; Analysis (calcd, found for C26H42O11): C (58.85, 58.79), H (7.98, 8.19).l,2,3,4,6-Penta-0-butanoyl-α-D-mannopyranose (α-ButsMannose): NMR (CDCl3) 1H-NMR (400 MHz): δ 5.87 (d, IH, J= 1.3), 5.48 (dd, IH, J= 3.4, J= 1.0), 5.31 (t, IH, J= 9.9), 5.14 (dd, IH, J= 9.9, J= 3.4), 4.25 (dd, IH, J= 12.4, J= 5.3), 4.15 (dd, IH, J= 12.4, J= 2.3), 3.79 (ddd, IH, J= 9.8, J= 5.2, J= 2.3), 2.42 (t, 2H, J= 6.8), 2.33-2.16 (m, 8H), 1.75-1.51 (m, 10H), 1.01-0.86 (m, 15H); 13C-NMR (100 MHz): δ 173.1, 172.6, 172.3, 172.1, 171.0, 90.2(1Jc-H = 163), 73.3, 70.5, 68.0, 65.1, 61.8, 35.9 (2C), 35.8, 35.7, 35.6, 18.5, 18.2 (2C), 18.1, 17.9, 13.6, 13.5 (3C), 13.4; MALDI-MS EPO (m/z): [M + Na]+ calcd for C26H42NaO11, 553.2619; found, 553.5510; Analysis (calcd, found for C26H42O11): C (58.85, 59.06), H (7.98, 8.12). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With pyridine at 20℃; for 12h; | |
With pyridine at 0 - 20℃; Inert atmosphere; | ||
With pyridine; dmap at 20℃; Cooling with ice; |
With pyridine at 0 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With iodine In water; acetic acid at 20℃; for 20h; | General procedure for synthesis of compounds 3a-l General procedure: A mixture of aldose (1 mmol), substituted-ortho-phenylenediamine (1.1 mmol) and iodine (0.1 mmol) in 10 mL AcOH (5N) was stirred at RT in open air. The reaction was complete in 3.5-20 hr indicated bythe TLC analysis. The reaction mixture was triturated with EtOAc to give precipitates, which were collected by filtration by using nylon membrane filter (Scheme 1). |
With iodine; acetic acid In methanol at 20℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: D-Mannose; 2,2-dimethoxy-propane With sulfuric acid In acetone at 0 - 20℃; for 24h; Stage #2: With triethylamine In acetone | 1.a1 PREPARATION EXAMPLE 1> Preparation of {3aR, AR, 6aS) -2, 2- Ddimethyltetrahydrothieno[3, A-d] [1, 3] dioxol-4-yl acetateStep ai. Preparation of {3aR, AR, 6R, 6aR) -6- (2, 2-dimethyl- 1, 3-dioxolan4~yl) -2, 2-dimethyl-tetrahydrofuro [3,4- d] [l,3]dioxol-4-olTo acetone (50 ml) were added D-mannose (1.74 g, 6.52 mmol) and 2, 2-dimethoxypropane (2.45 ml, 19.55 mmol) with stirring, followed by cooling the solution to 0 C. To the solution was dropwise added cone, sulfuric acid (0.45 g, 1.96 mmol) . The resulting reaction mixture was stirred at room temperature for 24 hrs, followed by neutralization with triethyl amine and concentration in a vacuum. The concentrate was purified by silica gel column chromatography using a mixture of hexane:ethylacetate (1:1, v/v) as an elution solvent to afford the object compound as a white solid (1.61 g, 95%) . m.p. 120.3-120.50C1H-NMR (CDCl3) ? 5.34 (s, 1 H), 4.76-4.79(m, 1 H), 4.58 (d, 1 H, J = 6.0 Hz), 4.34-4.39(m, 1 H), 4.15(dd, 1 H, J = 3.6, 7.2 Hz), 4.00-4.08 (m, 2 H); [?]25D 11.71 (c 0.11, CH2Cl2) ; FAB-MS m/z 261 [M + H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With iodine at 20℃; for 1h; optical yield given as %de; | |
100% | With pyridine; dmap at 0 - 20℃; | 2.1 3.2.1. 1,2,3,4,6-Penta-O-acetyl-α-d-mannopyranose.16a To a solution of d-mannose (21.6 g, 120.0 mmol, 1.0 equiv) in acetic anhydride (62.3 mL, 660.0 mmol, 5.5 equiv) at 0 °C were added DMAP (1.46 g, 12.0 mmol, 10 mol %) and pyridine (240 mL) and the mixture was allowed to warm to room temperature. The solution was stirred for 3 h and the reaction was quenched by addition of a 10% aqueous solution of CuSO4 (250 mL) and Et2O (250 mL). The two phases were separated and the organic layer was washed with a 10% aqueous solution of CuSO4 (5*150 mL) in order to remove pyridine. The organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure to afford 1,2,3,4,6-penta-O-acetyl-α-d-mannopyranose (46.5 g, quant.) as a white waxy solid. 1H NMR (400 MHz, CDCl3) δ 6.07 (d, J=1.8 Hz, 1H), 5.34-5.32 (m, 2H), 5.25-5.24 (m, 1H), 4.27 (dd, J=12.4, 4.9 Hz, 1H), 4.08 (dd, J=12.4, 2.5 Hz), 4.06-4.00 (m, 1H), 2.16 (s, 3H) 2.16 (s, 3H), 2.08 (s, 3H), 2.04 (s, 3H), 1.99 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 170.8 (s), 170.1 (s), 169.9 (s), 169.6 (s), 168.2 (s), 90.7 (d), 70.7 (d), 68.8 (d), 68.4 (d), 65.6 (d), 62.2 (t), 21.0 (q), 209.0 (q), 20.8 (3q). |
100% | With pyridine; dmap at 20℃; Inert atmosphere; |
100% | With pyridine; dmap at 0 - 20℃; | |
80.4% | With sulfuric acid at 0 - 20℃; for 0.666667h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With dmap In pyridine at 20℃; | 1,2,3,4,6-Penta-O-benzoyl-α-d-mannopyranoside (11a) A mixture of D-mannose (1.0 g, 5.55 mmol), benzoyl chloride (3.84 mL, 33.3 mmol) and DMAP (33.0 mg, 0.27 mmol) in anhydrous pyridine (11.0 mL) was stirred at room temperature overnight. It was then quenched with water and extracted with EtOAc. The combined organic layers were washed with 1 M aqueous HCl, water, saturated aqueous NaHCO3 and brine, dried over anhydrous Na2SO4, concentrated in vacuo. The residue was purified by silica gel chromatography to give 11a as a white solid (3.7 g, 95%). |
With pyridine at 20℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water; trifluoroacetic acid at 120℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: D-Mannose; edaravone With sodium hydroxide In methanol; water at 70℃; for 1.66667h; Stage #2: With hydrogenchloride In methanol; water at 20℃; | ||
With sodium hydroxide In methanol; water at 70℃; for 0.5h; | ||
With ammonia In methanol; water at 70℃; for 0.5h; | 2.4. Derivatization procedure General procedure: The procedure employed for the derivatization of monosaccharideswas carried out according to the method of Daotian, F et al.(Fu & Oneill, 1995) and modified by us. The hydrolysed polysaccharideor monosaccharides were dissolved in 5 ml ammonia. Then,the 100 μl solution was transferred into a clean tube, and 0.5 Mmethanol solution (100 μl) of PMP was added and mixed. The mixturewas allowed to react for 30 min at 70 °C, then cooled to ambienttemperature and was neutralized with 20 μl 1% glacial aceticacid. Water and chloroform (1.0 ml each) were added, and the mixturewas shaken vigorously. The chloroform layer was discarded,and the extraction process was repeated three times. Then, thesupernatant was centrifugated at 10,000 rpm for 10 min, whichwas collected for analysis directly or stored at -20 °C for laterLC/MS analysis. Scheme 1 shows the Glc derivatization reaction. |
In methanol at 70℃; for 0.5h; | Derivatization Treatment General procedure: The monosaccharides were dissolved in ammonia to prepare a solution with 1 mmol/L concentration. Then, the 450 L standard solution was mixed with a same volume of 0.5 M methanolsolution of PMP in a clean tube with stopper. The reaction occurs at 70 °C water-bath for 30 min andthen cool the mixture to normal temperature and neutralize with the amount of glacial acetic acid.Then chloroform (2.0 mL) was mixed. They were shaken vigorously, and the extraction process wasrepeated three times. The chloroform layer was abandoned and the supernatant was centrifuged at8000 rpm for 15 min. After filtering through 0.45 m nylon membrane, the sample was obtained forlater HPLC-MSn analysis. The hydrolytic polysaccharide was dissolved in 1 mL ammonia and derived with the same processes used in monosaccharide [21,23]. In this process, the ammonia solvent withoutany monosaccharide was used as blank control. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 41.1% 2: 9.2% | With water; 1-ethyl-3-methyl-1H-imidazol-3-ium chloride at 100℃; for 0.5h; | 7 EXAMPLE 7Conversion of CelluloseVarious Paired Metal Halide CatalystsEffect of elevated dissolution temperatures and reaction temperatures on conversion of carbohydrate polymers was investigated. Procedure of Example 2 was repeated. Various paired metal halide catalysts were used at various percent catalyst compositions. Loading of metal halide salts in the catalyst was held constant at 37 mmol/g ionic liquid. Various reaction parameters were employed. Results are presented in TABLE 8. TABLE 8 Run Number: 1 2 3 4 Mixed MetalCuCl2:CrCl2 CuCl2:CrCl3 CuCl2:CrCl3 CuCl2:PdCl2 Halide Catalyst (17:83) (83:17) (10:90) (83:17) (percent composition): Feed Cellulose Cellulose Cellulose Cellulose DTemp: 100° C. 100° C. 140° C. 100° C. DTime:1 hour 1 hour 0.5 hours 1 hour RTemp: 120° C. 120° C. 100° C. 120° C. RTime: 8 hours 1 hour 0.5 hours0.5 hours Product Yield (%) Cellobiose - 14.7 - 12.6 Glucose 0.38 40 2.0 43.6 Mannose 0.33 0.33 9.2 0.86 Sorbitol 0.69 1.04 0.52 0.86 1,6-Anhydro-β, - 1.73 3.4 3.2 D-Glucose Formic Acid - 0.03 1.0 1.7 Levulinic Acid 1.59 0.71 0.72 1.3 HMF 56 7.72 41.1 8.45 Total Yield 59 66.7 58.1 71.8 DTemp = Dissolution (Swell) Temperature; DTime = Dissolution Time; RTemp = Reaction Temperature; RTime = Reaction Time.Product yields in TABLE 8 do not total 100% due to presence of uncharacterized polymer residues. Results show that CrCl2 and CrCl3 as components of mixed metal catalysts are selective for HMF production with CrCl2 exhibiting the greater selectivity. For example, hydrolysis of cellulose using a [CUCl2:CrCl2] catalyst with a [17:83] percent catalyst composition occurs within 8 hours at a dissolution (swell) temperature of 100° C. (column 1). Here, 95% selectivity to HMF is observed among recovered products, with a yield for HMF of 56%. Using a [CuCl2:CrCl3] catalyst with a [10:90] percent catalyst composition, hydrolysis of cellulose occurs within 0.5 hours (column 3) at a dissolution (swell) temperature of 140° C., with a yield of HMF of 41%. In contrast, glucose is a predominant product obtained with paired metal halide catalysts including, e.g., [CuCl2:CrCl3] (column 2) and [CuCl2:PdCl2] (column 4), at a percent catalyst composition of [83:17], providing yields of glucose of 40 and 44%, respectively. As demonstrated, product selectivity and yields from a conversion reaction of carbohydrate polymers depend in part on dissolution temperature and time, reaction temperature, time of reaction, choice of catalyst, and mole ratios of the metal halides in the mixed metal catalyst. All parameters as will be selected by those of skill in the art in view of the disclosure are within the scope of the invention. No limitations are intended by discussion of the exemplary tests. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: D-Mannose With pyridine; acetic anhydride at 20℃; Inert atmosphere; Stage #2: 2-methyl-5-tert-butylthiophenol With boron trifluoride diethyl etherate In dichloromethane at 20℃; Inert atmosphere; | 5.7.4. (2-Methyl-5-tert-butylthiophenyl) 1-thio-α-d-mannopyranoside (9) To a solution of d-mannose (30 g, 167 mmol) in anhydrous pyridine (140 ml) was added under argon acetic anhydride (110 ml, 1.17 mol). The mixture was stirred overnight at room temperature then methanol (150 ml) was added and solvents were removed under reduced pressure. The residue was dissolved in CH2Cl2, washed with 1 M HCl and the aqueous layer was extracted with CH2Cl2. The combined organic layers were dried (MgSO4), filtered and concentrated. The residue was dissolved in dry CH2Cl2 (160 ml) under argon then 2-methyl 5-tert-butylthiophenol (46 ml, 250 mmol) and BF3·Et2O (64 ml, 505 mmol) were added. The solution was stirred overnight at room temperature then poured into satd aq NaHCO3 (250 ml). The aqueous layer was extracted with CH2Cl2 then the organic layer was dried (MgSO4), filtered and concentrated. The residue was purified by flash chromatography (cyclohexane/ethyl acetate: 1/1 then acetone) to yield 9 (43 g, 75%) as a white solid. Rf: 0.05 (cyclohexane/ethyl acetate: 1/1). -18 (c = 8, CHCl3) HRMS: [M+Na+] calculated for C17H26O5S 365.1399, found 365.1395. 1H NMR (400 MHz, CDCl3): 7.51 (d, 1H, Jortho-para = 2.0 Hz, Hortho), 7.19 (dd, 1H, Jpara-meta = 8.0 Hz, Jpara-ortho = 2.0 Hz, Hpara), 7.09 (d, 1H, Jmeta-para = 8.0 Hz, Hmeta), 5.44 (s, 1H, H-1), 4.82 (br s, 4H, OH), 4.27 (s, 1H, H-2), 4.11-4.03 (m, 3H, H-4, H-5, H-6a), 3.95 (d, 1H J3,4 = 5.7 Hz, H-3), 3.73 (d, 1H, Jgem = 11.9 Hz, H-6b), 2.33 (s, 3H, CH3), 1.27 (s, 9H, t-Bu). 13C NMR (400 MHz, CDCl3): 150.1 (qC Ar), 137.3 (qC Ar), 132.7 (qC Ar), 130.6 (Cortho), 130.4 (Cmeta), 125.5 (Cpara), 88.6 (C-1), 73.8 (C-4), 73.3 (C-2), 72.6 (C-3), 66.7 (C-5), 61.3 (C-6), 34.8 (qC t-Bu), 31.7 (3C, t-Bu), 20.7 (CH3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 20℃;pH 7.4;aq. phosphate buffer;Kinetics; | General procedure: All reagents were purchased from Aldrich and Frontier Scientific. For thermodynamic binding experiments, an RF-1501 Shimadzu fluorometer was used. For stopped-flow experiments, an Applied Photophysics RX2000 Rapid Mixing stopped-flow unit with FluoromaxIIII fluorometer (Horiba) was used. The dead time for this instrument is 0.05 s. All kinetic experiments were conducted in phosphate buffer (0.1 M) at pH 7.4 and at room temperature. Kinetic measurements were performed under pseudo first-order conditions. In a fixed concentration of IQBAs, different concentrations of sugars were mixed within a short time period. All the reaction curves were fitted using formula (1) in Origin 8. Using formula (2), Kobs can be calculated. Values for kon and koff were calculated using formula (3) by varying [S], the substrate concentration. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 20℃;pH 7.4;aq. phosphate buffer;Kinetics; | General procedure: All reagents were purchased from Aldrich and Frontier Scientific. For thermodynamic binding experiments, an RF-1501 Shimadzu fluorometer was used. For stopped-flow experiments, an Applied Photophysics RX2000 Rapid Mixing stopped-flow unit with FluoromaxIIII fluorometer (Horiba) was used. The dead time for this instrument is 0.05 s. All kinetic experiments were conducted in phosphate buffer (0.1 M) at pH 7.4 and at room temperature. Kinetic measurements were performed under pseudo first-order conditions. In a fixed concentration of IQBAs, different concentrations of sugars were mixed within a short time period. All the reaction curves were fitted using formula (1) in Origin 8. Using formula (2), Kobs can be calculated. Values for kon and koff were calculated using formula (3) by varying [S], the substrate concentration. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 20℃;pH 7.4;aq. phosphate buffer;Kinetics; | General procedure: All reagents were purchased from Aldrich and Frontier Scientific. For thermodynamic binding experiments, an RF-1501 Shimadzu fluorometer was used. For stopped-flow experiments, an Applied Photophysics RX2000 Rapid Mixing stopped-flow unit with FluoromaxIIII fluorometer (Horiba) was used. The dead time for this instrument is 0.05 s. All kinetic experiments were conducted in phosphate buffer (0.1 M) at pH 7.4 and at room temperature. Kinetic measurements were performed under pseudo first-order conditions. In a fixed concentration of IQBAs, different concentrations of sugars were mixed within a short time period. All the reaction curves were fitted using formula (1) in Origin 8. Using formula (2), Kobs can be calculated. Values for kon and koff were calculated using formula (3) by varying [S], the substrate concentration. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid In N,N-dimethyl-formamide at 20℃; | O-benzyl-2,3-O- isopentylidene-5-α-D-lyxomannofuranoside(6) D-Mannose (3.60g, 20 mmol) was dissolved in DMF (30 mL) and then 3-pentanone (40 mL) was added into the solution. Conc. sulfuric acid (1 mL) was slowly added into the mixture and stirred for overnight at the room temperature. After that the pH of the solution was adjusted to be neutral by using 10% aq. sodium carbonate (30 mL) and then extracted with CH2Cl2. The organic layers were collected, dried (anh.Na2SO4) and the solvent was removed under reduced pressure to afford crude 2,3:5,6-di-O-isopentyliden-5-a-Dmannofuranone (4.21 g) which was used in the next step without further purification. | |
1.14 g | With sulfuric acid In N,N-dimethyl-formamide at 0 - 20℃; | Preparation of benzyl-2,3-O-isopentylidene-and 2,3-O-benzylidene-a-D-mannofuranosides General procedure: A solution of d-mannose (1.00 g, 5.55 mmol) in dry DMF (11 mL) was mixed with 3-pentanone (5.50mL) or benzaldehyde (5.50 mL). The mixture was cooled to 0°C and concd H2SO4 (0.28 mL) was added dropwise to the mixture. The reaction was stirred for 12 h then it was neutralized with aqueous NaHCO3. The mixture was extracted with CH2Cl2. The organic layer was collected, dried over Na2SO4, filtered and the filtrate was concentrated by evaporation under reduced pressure. The residue was used in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: <i>O</i>1-β-D-mannopyranosyl-D-mannitol With hydrogenchloride In water at 80℃; for 2h; Stage #2: In water | A mixture of 1 (10.0 mg) and sodium methoxide (NaOMe, 3.4 mg) in MeOH (0.8 mL) was kept at room temperature for 1 h. The reaction mixture was diluted with MeOH (4 mL), and to the solution was added Amberlite IRA400 J CL (Cl form, 500 mg). After 5 h, the resin was removed by filtration, and evaporation of the solvent under reduced pressure yielded the corresponding deacylated product. The crude product was dissolved in 2.5% hydrochloric acid (0.8 mL), and the resulting mixture was heated at 80 C for 2 h. The reaction mixture was neutralized with Amberlite IRA400J CL (OH form). After filtration, the filtrate was concentrated in vacuo. The NMR spctroscopic properties of the product were in accord with those of a 1:1 mixture of D-mannose and D-mannitol. To a solution of the residue in H2O (0.4 mL) was added sodium borohydride (7 mg) at room temperature for 2 h, the reaction mixture was quenched with acetone and concentrated in vacuo. To the dry residue, pyridine (0.5 mL) and acetic anhydride (0.5 mL) were added and the mixture was heated at 100 C for 3 h. After removing pyridine and acetic anhydride by nitrogen blow, the residue was dissolved in chloroform (l mL). The chloroform solution was washed with water (1 mL) three times, dried with anhydrous sodium sulfate, and filtrated. The filtrate was evaporated to produce pale brown oil, which was subjected to GC analysis |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroacetic acid at 120℃; for 3h; | 2.2 Extraction, isolation and purification of polysaccharide The polysaccharide was hydrolyzed by 2M TFA at 120°C for 3h into monosaccharides under airtight condition, and the monosaccharides were conventionally converted into the alditol acetates as described (Xin et al., 2012) and were analyzed by gas chromatography (GC, Agilent 6890, USA) equipped with a HP-5 column (30m×0.25mm×0.25μm) and flame-ionization detector (FID). The operation was performed using the following conditions: 160°C for 2min, then to 200°C at 6°C/min, then to 215°C at 0.2°C/min, then to 240°C at 6°C/min for 30min. Nitrogen was used as the carrier gas at 1mL/min; injection temperature was 250°C; detector temperature was 300°C. Monosaccharides identification was done by comparison with reference monosaccharides. The relative molar proportions were calculated by the area normalization method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With acetic acid In ethanol for 6h; Reflux; | General procedure for preparation of spiro{(2H,3H)-3-[(1-(E)-polyhydroxyalkylidene)-imino]quinazoline-2,1-cyclohexan}-4(1H)-ones(7a-c) General procedure: A mixture of compound 6 (2.31 g, 10 mmol)and the appropriate linear sugar namely: D-xylose,D-arabinose and D-mannose (10 mmol) in absoluteethanol in the presence of few drops of glacial aceticacid was refluxed for 6 h. The reaction mixture wascooled and the formed precipitate was filtered offand recrystallized from isopropanol to obtain thedesired Schiffs bases 7a-c, respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium tris(acetoxy)borohydride; acetic acid In water at 20℃; for 48h; | 2.3 Synthesis of M-chitosan M-chitosan was synthesized as described by Yalpani and Laurance (1984) with little modification. Mannose conjugation was carried out by reductive amination of chitosan with d-mannose in the presence of sodium triacetoxyborohydride [NaBH(OAc)3] (reductive amination reagent). In brief, chitosan was dissolved with stirring in 1% aqueous acetic acid of pH 5.5. An aqueous solution of d-mannose and sodium triacetoxyborohydride was prepared. This solution was then, added to the resulting viscous solution of chitosan while stirring slowly and left at room temperature for 2 days. The products were dialyzed against double distilled water in a dialysis tube (MWCO 12-14kDa; Himedia, India) for 72h followed by lyophilization. The chemical structure of M-chitosan was elucidated through FT-IR (Schimadzu, Model 8400, Japan) and 1H NMR (Jeol AL300 FT-NMR) spectroscopy. FT-IR spectroscopy was carried out using the KBr disk method after adsorption of a smaller amount of substance on KBr and recorded over the range of 4000-400cm-1. 1H NMR spectroscopy was carried out in the pulsed FT mode at a 300MHz resonance frequency for protons after dissolving samples in deuterated DMSO. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroacetic acid; In water; at 100℃; for 8h;Sealed tube; | A simple and sensitive high performance liquid chromatographic method was applied to the simultaneous determination of nine kinds of monosaccharides (glucose, rhamnose, mannose, arabinose, galactose, xylose, ribose, galacturonic acid and N-acetyl-d-glucosamine) in FAAP-02 by pre-column derivatization with 1-phenyl-3-5-pyrazolone (PMP) as described previously with proper modification (Lv et al., 2009). In brief, FAAP-02 was hydrolyzed with TFA (3M) for 8h at 100C in a sealed ampoule. After cooling to room temperature, the reaction mixture was centrifuged and the supernatant was collected and lyophilized. The hydrolyzed sample or monosaccharide standard aqueous solution was mixed with aqueous NaOH (0.25M) and PMP methanol solution (0.25M) thoroughly. Then each mixture was incubated at 70C for 90min. After cooled and neutralized with HCl (0.25M), the resulting solution was extracted with chloroform to remove the excess reagents. The aqueous layer was filtered through a 0.45mum membrane before detection. The analysis of PMP-labeled monosaccharides was performed on an Agilent 1260 HPLC system equipped with a ZORBAX Eclipse XDB-C18 (250mm×4.6mm, id: 5mum, column temperature: 30C). The wavelength of detection was 250nm. Elution was carried out with a mixture of acetonitrile and phosphate buffer (0.06M, pH 6.8) in a ratio of 17: 83 (v/v, %) at a flow rate of 1mL/min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With pyridine; 1,1,1,3,3,3-hexamethyl-disilazane at 75℃; for 1.5h; Inert atmosphere; | 17ter Silylation of mannose α-D-mannose (leq) was dissolved in pyridine, under argon atmosphere and magnetical stirring. HMDS (8.6eq)and TMSC1 (7.12 eq) were added and the mixture became white.the mixture was heated to 75°C during 90min, then quenched by water and extracted by pentane, dried on MgS04, and concentrated under vacuum. Several co-evaporations were done to remove pyridine residues. The white oil was used without further purification. |
64% | With pyridine at 0 - 23℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63.9% | With Hβ zeolite at 160℃; for 18h; | |
46% | With aluminum(III) sulphate octadecahydrate at 160℃; for 2.5h; Inert atmosphere; | 18 12 g of methanol, 1.72 mmol of glucose and 0.34 mmol of Al2 (S4) 3 · 18H20 were charged into an autoclave and heated to 160 ° C,Reaction 2.5 h.The sugar conversion was determined by liquid chromatography analysis,The glucose conversion was 100%.The reaction products were analyzed by gas chromatography-mass spectrometry (GC-MS) and compared with methyl levulinate standard. The results showed that the main product was methyl levulinate.The yield of methyl levulinate was 67%.The same conditions as in Example 2 were obtained except that mannose was substituted for glucose, and the mannose conversion was 100%, And the molar yield of methyl levulinate was 46%. |
53 %Chromat. | With HY-6 at 150 - 160℃; for 20h; Autoclave; Inert atmosphere; | 3a-d General procedure: A 50 ml autoclave (Microclave reactor from Autoclave Engineers) was charged with 250 mg of mannose, 150 mg of a catalyst (HY 6, Hbeta 19), and 10 ml solvent (methanol, ethanol) and then pressurized with argon (20 bar). The autoclave was heated to 160 °C and the stirring was started once the temperature reached 150 °C (300 rpm). After 20 hours ofstirring, the autoclave was quenched with cold water, 50 mg naphthalene (internal standard) added and the reaction mixture analyzed as described in examples 1. The results are shown in the Tables 5 and 6. |
With Amberlyst-15; Sn-beta (125) at 160℃; for 5h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With iodine In water; acetic acid at 20℃; for 16h; | General procedure for synthesis of compounds 3a-l General procedure: A mixture of aldose (1 mmol), substituted-ortho-phenylenediamine (1.1 mmol) and iodine (0.1 mmol) in 10 mL AcOH (5N) was stirred at RT in open air. The reaction was complete in 3.5-20 hr indicated bythe TLC analysis. The reaction mixture was triturated with EtOAc to give precipitates, which were collected by filtration by using nylon membrane filter (Scheme 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroacetic acid at 110℃; | 2.1.2 Extraction, purification and isolation of polysaccharide We detected the composition and content of monosaccharide in TPPPS by precolumn derivatization ultra-high performance liquid chromatography-tandem quadrupole mass spectrometry. TPPPS was cleaned with C18 SPE cartridge, and then hydrolysised with TFA at 110°C. The products were derivated with 50μL 0.2mol/L 1-phenyl-3-methyl-5-pyrazolone (PMP) for 30min. The obtained monosaccharides were separated at a flow rate of 0.5mL/min on a Waters ACQUITY UPLC BEH C18 column (2.1mm i. d.×50mm, 1.7μm) at 37°C, by using acetonitrile and buffered salt solution (0.5mmol/L ammonium acetate and 0.05% acetic acid) as the mobile phase in the gradient elution. The analysis of target compounds was performed in multiple reaction monitoring (MRM) mode via positive electrospray ionization, and quantified by the internal standard method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With sulfonated polystyrene cation exchange resin CAT600 at 40℃; for 3h; Green chemistry; | General Procedure for the O-Isopropylidenation. General procedure: To asuspension of the substrate (2 mmol) in dry acetone (10 mL),CAT600 (100 mg) was added. Then the mixture was stirred at 40 °C till the TLC (n-hexane-EtOAc 2:1) showed the completion of the reaction. The catalyst was separated by filtration, washed with acetone, dried, and reused for a consecutive run under the same reaction conditions. The filtrate was condensed to dry in vacuum, and the residue was dissolved in CH2Cl2 (10 mL) and washed with 3 × 5 mL brine.The organic layer was dried over anhydrous Na2SO4, filtered and evaporated to afford the crude product. Then the desired pure product was obtained by recrystallization from n-hexane. While, the silica gel column chromatography was used if the product existed in the liquid form. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With acetic acid In ethanol; water for 4h; Reflux; | General procedure: The acetylhydrazone 3(1.20 g, 5 mmoles) dissolved in ethanol (15 mL) was added to a solution of the respective monosaccharide(5 mmoles) in water (1 mL) and glacial aceticacid (1 mL). The mixture was heated under refluxfor 4 h and the resulting solution was concentratedand left to cool. The formed precipitate was filteredoff, washed with water and ethanol, then dried andrecrystallized from ethanol to afford 4-6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With acetic acid In ethanol; water Reflux; | (Z)-3-(4-Methoxybenzyl)-5-(hydrazinylsugar)-3H-[1,2,3]triazolo[4,5-d]pyrimidin-7(6H)-one(12a-c) General procedure: To a well-stirred solution of the respectivemonosaccharide (0.01 mol) in water (2 mL), andglacial acetic acid (0.2 mL) was added the hydrazinederivative 11 (10 mmol) in ethanol (15 mL). Themixture was heated under reflux for 4-6 h (TLC) andthe resulting solution was concentrated and left tocool. The precipitate formed was filtered off,washed with water, then dried and crystallized fromethanol-DMF (2 : 1, v/v) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: D-Mannose With sodium hydride In N,N-dimethyl-formamide; mineral oil at 5℃; for 1.16667h; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide; mineral oil for 24.5h; Inert atmosphere; | Benzyl 2,3,4,6-tetra-O-benzyl-β-D-mannopyranoside D-Mannose (5 g, 27.8 mmol) was suspended in 100 mL anhydrous DMFin a 250 mL round-bottom flask. The reaction vessel was flushed with argon and cooled in an ice bath to 5C. NaH (60% dispersion in mineral oil; 6.6 g,166.5 mmol) was then added over a period of 10 min. This was allowed tostir for 60 min followed by the addition of BnBr (19.8 mL, 166.5 mmol) overa 30-min period and stirring continued for 24 h. Methanol (20 mL) was thenadded to the reaction and the DMF removed under high vacuum. The cruderesidue was dissolved in CH2Cl2 (100 mL), transferred to a separatory funnel,and washed with H2O (3 × 150 mL). The organic layer was dried over anhydroussodium sulphate and filtered. The filtrate was concentrated in vacuoand the crude residue subjected to purification by column chromatographyusing petroleum ether/ethyl acetate (gradient elution) to afford 2 (13.65 g,78%); Rf (EtOAc : Pet. Ether; 2:3) = 0.57; 1H NMR (600 MHz, CDCl3): δ: 3.45(1H, ddd, J4,5 = 9.5 Hz, J5,6a = 2.0, J5,6b = 6.0 Hz, H-5), 3.49 (1H, dd, J2,3 =5.6 Hz, J3,4 = 9.5 Hz, H-3), 3.78 (1H, dd, J5,6b = 6.0 Hz, J6a,6b = 10.8, H-6b),3.83 (1H, dd, J5,6a = 2.0 Hz, J6a,6b = 10.8, H-6a), 3.90 (1H, t, J3,4 = 9.5 Hz,J4,5 = 9.5 Hz, H-4), 3.92 (1H, dd, J1,2 = 3.7 Hz, J2,3 = 5.6 Hz, H-2), 4.43, 4.50(2H, ABq, J = 11.8 Hz, PhCH2O-), 4.44 (1H, s, H-1), 4.54, 4.90 (2H, ABq, J =10.8 Hz, PhCH2O-), 4.59, 5.00 (2H, ABq, J = 12.0 Hz, PhCH2O-), 4.60, 4.65(2H, ABq, J = 12.1 Hz, PhCH2O-), 4.89, 5.01 (2H, ABq, J = 12.3 Hz, PhCH2O-), 7.18-7.46 (25H, m, Ar-H); 13C NMR (150 MHz, CDCl3): δ: 69.8 (1C, C-6), 71.0(1C, PhCH2O), 71.6 (1C, PhCH2O), 73.6 (1C, PhCH2O), 73.9 (1C, PhCH2O),74.0 (1C, C-4), 75.0 (1C, C-2), 75.2 (1C, PhCH2O), 76.1 (1C, C-5), 82.5 (1C, C-3),100.4 (1C, JC1-H1 = 152.4 Hz, C-1), 127.6-128.5 (25C, Ar-C), 137.6 (1C, Arquat),138.3 (1C, Ar-quat), 138.5 (1C, Ar-quat), 138.6 (1C, Ar-quat), 138.9 (1C,Ar-quat). HRMS calculated for C41H42O6Na: 653.2879; found: 653.2874 (M +Na)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 22% 2: 7% 3: 6% | With 0.06-Fe/β zeolite In water at 150℃; for 1.5h; Autoclave; High pressure; Inert atmosphere; Green chemistry; | 4.2. Catalytic runs General procedure: The conversion of glucose to fructose was conducted a 100 mL high-pressure autoclave at the desired temperature with stirring speed of 500 rpm. The reactor was pressurized at 5 bar of N2 and heated to the desired reaction temperature. Once the reaction temperature was reached, the monitoring of the reaction started. After the reaction was completed, the mixture was cooled to room temperature. All samples were filtered before further analysis using HPLC. |
With water at 140℃; for 2h; Inert atmosphere; | ||
With lithium bromide trihydrate In water at 130℃; for 1h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 32% 2: 20.6% 3: 7.1% | With water at 160℃; for 1.5h; Autoclave; Inert atmosphere; | 3.2. Catalytic reaction General procedure: Cellobiose hydrolysis was carried out in a steal autoclave witha Teflon liner (50 mL), equipped with a magnetic stirrer. Typi-cally, 0.20 g cellobiose, 0.1 g catalyst, and 20 mL H2O were added.Then, the system was sealed and flushed with nitrogen for severaltimes and finally pressurized to 2.5 MPa in nitrogen. The reactionswere carried out at 160C for 90 min with magnetic stirring at600 r/min. After reaction, the solid catalyst was separated by cen-trifugation. The liquid phase was analyzed by high performanceliquid chromatography (HPLC) equipped with an ICSep ICE-Coregel87H3 column and a RID detector. The HPLC column was retainedat 38C, using H2SO4solution (5 mM, 0.6 mL/min) as the mobilephase. The yields were calculated as the molar ratio of the prod-uct and the initial cellobiose, corrected by the number of carbonatoms[20]. The products were qualified by injection of standardsamples and quantified by application of calibration curves pre-pared by using external standards (See the detail in the supportinginformation). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 17.3% 2: 6.9% 3: 6.8% | With water at 160℃; for 1.5h; Autoclave; Inert atmosphere; | 3.2. Catalytic reaction General procedure: Cellobiose hydrolysis was carried out in a steal autoclave witha Teflon liner (50 mL), equipped with a magnetic stirrer. Typi-cally, 0.20 g cellobiose, 0.1 g catalyst, and 20 mL H2O were added.Then, the system was sealed and flushed with nitrogen for severaltimes and finally pressurized to 2.5 MPa in nitrogen. The reactionswere carried out at 160C for 90 min with magnetic stirring at600 r/min. After reaction, the solid catalyst was separated by cen-trifugation. The liquid phase was analyzed by high performanceliquid chromatography (HPLC) equipped with an ICSep ICE-Coregel87H3 column and a RID detector. The HPLC column was retainedat 38C, using H2SO4solution (5 mM, 0.6 mL/min) as the mobilephase. The yields were calculated as the molar ratio of the prod-uct and the initial cellobiose, corrected by the number of carbonatoms[20]. The products were qualified by injection of standardsamples and quantified by application of calibration curves pre-pared by using external standards (See the detail in the supportinginformation). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | Stage #1: D-Mannose; 3-(2-aminoethoxy)benzyl 2-methylpropanethioate hydrochloride With sodium cyanoborohydride; acetic acid In methanol at 50℃; for 6h; Stage #2: With hydrogenchloride In water | 4.15 Preparation of S-3-(2-(bis((2R,3R,4R,5R)-2,3,4,5,6- pentahydroxyhexyl)amino)ethoxy)benzyl 2-methylpropanethioate hydrochloride (15); A solution of amine 13 (935 mg, 3.20 mmol) in methanol (50 mL) was charged with D- mannose (2.30 g, 12.7 mmol) and acetic acid (0.76 mL, 12.7 mmol) followed by sodium cyanoborohydride (800 mg, 12.7 mmol) and the resulting reaction mixture was heated and stirred at 50 °C for 4 h. Additional, D-mannose (0.58 g, 3.20 mmol), acetic acid (0.19 mL, 3.20 mmol), and sodium cyanoborohydride (200 mg, 3.20 mmol) were added and the resulting reaction mixture was heated at 50 °C for another 1 h. After 1 h additional D- mannose (0.58 g, 3.20 mmol), acetic acid (0.19 mL, 3.20 mmol), and sodium cyanoborohydride (200 mg, 3.20 mmol) were added and the resulting mixture was heated at |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24% | Stage #1: D-Mannose; 3-(2-aminoethoxy)benzyl ethanethioate hydrochloride With sodium cyanoborohydride; acetic acid In methanol at 50℃; for 6h; Stage #2: With hydrogenchloride In water | 6.18 6. Preparation of S-3-(2-(bis((2R,3R,4R,5R)-2,3,4,5,6- pentahydroxyhexyl)amino)ethoxy)benzyl ethanethioate (18); A solution of amine 16 (835 mg, 3.20 mmol) in methanol (50 mL) was charged with D- glucose (2.30 g, 12.7 mmol) and acetic acid (0.76 mL, 12.7 mmol) followed by sodium cyanoborohydride (800 mg, 12.7 mmol) and the resulting mixture was heated at 50 C for 4 h. Additional, D-glucose (0.58 g, 3.20 mmol), acetic acid (0.19 mL, 3.20 mmol), and sodium cyanoborohydride (200 mg, 3.20 mmol) were added and the resulting mixture heated at 50 C for 1 h. A second equivalent of D-mannose (0.58 g, 3.20 mmol), acetic acid (0.19 mL, 3.20 mmol), and sodium cyanoborohydride (200 mg, 3.20 mmol) were added and the resulting mixture was heated at 50 °C for 1 h. The reaction mixture was cooled to rt and water was added; after solvent was removed under reduced pressure, more water was added and a solid precipitated out and was filtered washing with water/methanol to get the boron complex of the free base 18. The free base complex was then acidified with 4 N HC1 in water to make HCL salt and lyophilized to get 18 (90% pure by HPLC) as an off-white solid. The solid was further purified by reverse-phase chromatography using a CI 8 Gold column to get 18 (450 mg, 24%) as a white solid and an additional 1.00 g of 18, <95% purity by HPLC, was isolated as well. 1H NMR (400 MHz, CD3OD) δ 7.22 (t, J = 7.8 Hz, 1H), 6.99-6.97 (m, 1H), 6.95- 6.90 (m, 2H), 4.42-4.37 (m, 2H), 4.19-4.1 1 (m, 2H), 4.09 (s, 2H), 3.94-3.61 (m, 14H), 3.55- 3.44 (m, 2H), 2.32 (s, 3H); 1H NMR (400 MHz, DMSO-6) δ 8.42 (brs, 1H), 7.25 (t, J = 7.9 Hz, 1H), 6.93-6.86 (m, 3H), 5.71-5.57 (m, 1H), 5.54-5.42 (m, 1H), 4.92^.15 (m, 1 1H), 4.09 (s, 2H), 4.05-3.87 (m, 3H), 3.77-3.21 (m, 14H), 2.35 (s, 3H); ESI MS m/z 554 [C23H39NOi2S + H].+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Stage #1: D-Mannose; S-3-(2-aminoethoxy)benzyl propanethioate hydrochloride With sodium cyanoborohydride; acetic acid In methanol at 50℃; for 6h; Stage #2: With hydrogenchloride In water | 10.25 10. Preparation of S-3-(2-(bis((2R,3R,4R,5R)-2,3,4,5,6- pentahydroxyhexyl)amino)ethoxy)benzyl propanethioate hydrochloride (25); A solution of amine 23 (880 mg, 3.20 mmol) in methanol (50 mL) was charged with D- mannose (2.30 g, 12.7 mmol) and acetic acid (0.76 mL, 12.7 mmol) followed by sodium cyanoborohydride (800 mg, 12.7 mmol) and the resulting mixture was heated and stirred at 50 °C for 4 h. Additional, D-mannose (0.58 g, 3.20 mmol), acetic acid (0.19 mL, 3.20 mmol), and sodium cyanoborohydride (200 mg, 3.20 mmol) were added and the resulting reaction mixture was heated at 50 °C for 1 h. An additional portion of D-mannose (0.58 g, 3.20 mmol), acetic acid (0.19 mL, 3.20 mmol), and sodium cyanoborohydride (200 mg, 3.20 mmol) were added and the resulting mixture was heated at 50 C for 1 h. The reaction mixture was cooled to rt and water was added (20 mL); after solvent was removed under reduced pressure, additional water (20 mL) was added and the resulting solid was filtered, washed with water/methanol to afford the free base of 25. The free base was then acidified with 4 N HC1 in water to make HCL salt and lyophilized to get 25 (1.30 g, 67%) as an off- white solid: NMR (400 MHz, CD3OD) δ 7.25 (t, J = 7.8 Hz, 1H), 7.00-6.96 (m, 1H), 6.96-6.90 (m, 2H), 4.44^.11 (m, 2H), 4.22-4.1 1 (m, 2H), 4.10 (s, 2H), 3.94-3.61 (m, 14H), 3.57-3.44 (m, 2H), 2.59 (q, J = 7.9 Hz, 2H), 1.15 (t, J = 7.9 Hz, 3H); 1H NMR (400 MHz, DMSO-c δ 8.74 (brs, 1H), 7.24 (t, J = 8.1 Hz, 1H), 6.98-6.88 (m, 3H), 5.02-4.46 (m, 5H), 4.45-4.30 (m, 4H), 4.23-3.89 (m, 8H), 3.84-3.19 (m, 16H), 2.61 (q, J= 7.8 Hz, 2H), 1.08 (t, J= 7.8 Hz, 3H); ESI MS m/z 568 [C24H4.NO12S + H].+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sodium cyanoborohydride; acetic acid In methanol at 20 - 55℃; for 6h; | 14.57 Preparation S-4-(2-(bis((2R,3R,4R,5R)-2,3,4,5,6-pentahydroxyhexyl)amino)ethoxy)benzyl 2-methylpropanethioate (57); A solution of amine 55 (1.50 g, 5.92 mmol) in methanol (75 mL) was charged with Dmannose (2.13 g, 11.8 mmol) and acetic acid (0.72 mL, 11.8 mmol) followed by sodium cyanoborohydride (735 mg, 11.8 mmol) and the resulting mixture was stirred at room temperature for 2 h at 55 °C. Additional D-mannose (1.07 g, 5.93 mmol), AcOH (0.36 mL, 5.93 mmol), and sodium cyanoborohydride (368 mg, 5.93 mmol) were charged and the mixture was stirred for 2 h at 55 °C. Further additional D- mannose (1.07 g, 5.93 mmol), AcOH (0.36 mL, 5.93 mmol), and sodium cyanoborohydride (368 mg, 5.93 mmol) were charged and the mixture was stirred for 2 h at 55 °C. After the solvent was removed the reaction mixture was crystalized from water: methanol (100:20 mL), to afford the boron complex of the free base 57 (2.25 g, 66%) as a white solid. ESI MS m/z 582 [M + H]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium acetate In water at 20℃; | 6 4.2 General procedure for tetrazanes General procedure: 2,4-Diisopropylcarbonohydrazide bis-hydrochloride (2mmol) and the aldose (2mmol) were dissolved in a minimum amount of water. To this solution was added 4mmol of sodium acetate dissolved in water. The solution was stirred at room temperature for 4-6h. After this period, the mixture was extracted four times with an equal volume of 1-butanol. The combined butanol layers were dried with sodium sulfate, filtered and evaporated to give the crude yellow aldose-tetrazane. The crude compound was washed with hot hexane or heptane to leave an off-white aldose-tetrazane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With acetic acid In ethanol for 5h; Reflux; | General procedure for the synthesis of sugar hydrazone derivatives 20 a-e General procedure: To a solution of hydrazinophthalazine 3 (0.1 mol) in ethanol (50 mL) was added the respective sugar (0.1 mol) and catalytic amount of glacial acetic acid (0.1 mL). The mixture was heated under reflux on a water bath for 5 h. After cooling the separated solid was collected by filtration, dried and crystallized from the appropriate solvent to give 20 a-e. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With acetic acid In ethanol Reflux; | General procedure for synthesis of N-(glycosylidene hydrazone) derivatives 2a-e General procedure: A mixture of compound 1 (10 mmol), appropriate monosaccharides, namely Dglucose,D-galactose, D-mannose, D-xylose, or L-arabinose (10mmol) and catalyticamounts of glacial acetic acid were heated at reflux in absolute ethanol (30 mL) for 2-4 h. The reaction mixture was allowed to cool to room temperature and the precipitateformed was filtered off, washed with ethanol, dried, and crystallized fromethanol to afford title compounds 2a-e. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sodium cyanoborohydride; acetic acid In methanol at 55℃; for 5h; | 49 Preparation of S,S'-((6-(2-(bis((2R,3R,4R,5R)-2,3,4,5,6- pentahydroxyhexyi)amino)ethoxy)naphthalene-2,3-diyl)his(methylene)) diethanethioate hydrochloride (99) A solution of amine 98 (1.10 g, 2.75 mmol) in methanol (35 mL) was charged with D- mannose (2.00 g, 1 1.0 mmol) and acetic acid (0.66 mL, 1 1.0 mmol) successively followed by Sodium cyanoborohydride (700 mg, 1 1.0 mmoi) and the resulting reaction mixture was heated 55 °C and stirred at 55 °C for 2 h. Additional, D-mannose (498 mg, 2.75 mmol ) and acetic acid (0.17 mL, 2.75 mmol) followed by sodium cyanoborohydride (1.0 equiv) and the resulting reaction mixture was heated stirred at 50 °C for another 1 h. Further additional, D- mannose (1.0 equiv) and acetic acid (1.0 equiv) successively followed by sodium cyanoborohydride (173 mg, 2.75 mmol) and the resulting reaction mixture was heated stirred at 55 °C for another 2 h. Reaction mixture was cooled to rt and water was added; solid precipitation came out which was filtered through filter paper and washed with water/methanol to get free base of 12 (1.25 g, 66%) as a off white solid. 1.00 g of free base 99 was then acidified with 4 N HCl in water to make HCL salt and was purified by reverse phase column (twice) to get 135 mg (13%) of HCl salt 99 as an off-white solid. lU NMR (400 MHz, CD3OD) δ 7.75 (s, 2H), 7.71 (d, J = 8.6 Hz, 1H), 7.27 (d, J = 2.5 Hz, 1 H), 7.23 (dd, J 8.6, 2.5 Hz, 1H), 4.57-4.49 (m, 2H), 4.327 (s, 2H), 4.322 (s, 2H), 4.21- 4.10 (m, 2H), 4.01-3.58 (m, 14H), 3.58-3.46 (m, 2H), 2.349 (s, 3H), 2.345 (s, 3H). ; FontWeight="Bold" FontSize="10" H NMR (400 MHz, DMSO- δ 7.80 (s, 1 H), 7.78 (d, J = 8.8 Hz, 1 H), 7.76 (s, 1 H), 7.32 (d, J = 2.4 Hz, 1H), 7.23 (dd, J = 8.8, 2.4 Hz, 1H), 5.68 (d, J = 6.5 Hz, 1H), 5.47 (d, J = 6.5 Hz, 1 H), 4.70 (brs, 1 H), 4.63-4.34 (m, 6H), 4.29 (s, 4H), 4.07-3.88 (m, 2H), 3.82-3.74 (m, 2H), 3.69-3.18 (m, 17H), 2.38 (s, 3H), 2.37 (s, 3H); ESi MS m/z 692 [C30H4SNO 13S2 + H] +. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | Stage #1: D-Mannose; S,S'-((4-(2-aminoethoxy)-1,2-phenylene)bis(methylene)) diethanethioate hydrochloride With sodium cyanoborohydride; acetic acid In methanol at 55℃; for 12h; Stage #2: With hydrogenchloride In water | 23 23. Preparation otS '-((4-(2-(bis((2R,3Rt4R,5R)-2t3,4,5,6- pentahydrox hex l)amino)ethoxy)-l,2-phenylene)bis(methylene)) diethanethioate hydrochloride (68) A solution of amine 9 (800 mg, 2.28 mmol) in methanol (120 mL) was charged with D- mannose (1.23 g, 6.85 mmol) and acetic acid (41 1 mg, 6.85 mmol ) successively followed by sodium cyanoborohydride (430 mg, 6.85 mmol) and the resulting reaction mixture was stirred at 55 °C for 3 h. Additional D-mannose (820 mg, 4.53 mmol), acetic acid (274 mg, 4,53 mmol) and sodium cyanoborohydride (286 mg, 4.53 mmol) were added and continued to be stirred at 55 °C for 2 h. Additional D-mannose (820 mg, 4.53 mmol), acetic acid (274 mg, 4.53 mmol) and sodium cyanoborohydride (286 mg, 4.53 mmol) were added and continued to be stirred at 55 °C for 3 h. Additional D-mannose (820 mg, 4.53 mmol), acetic acid (274 mg, 4.53 mmol) and sodium cyanoborohydride (286 mg, 4.53 mmol) were added and continued to be stirred at 55 °C for 4 h. Water (30 mL) was added and the resulting mixture was kept in fridge for 16 h. The precipitated yellow solid was collected by filtration, to afford 1.20 g of compound 1 1 with 90% purity as free base. The solid acidified with 1 N HC1, to make HC1 salt solution and purified by reverse-phase chromatography, to afford compound 68 (791 mg, 51%) as an off-white solid: *H NMR (400 MHz, CD3OD) δ 7.25 (d, J = 8.8 Hz, 1H), 6.99 (d, J = 2.4 Hz, 1 11 ), 6.89 (dd, J = 8.8, 2.4 Hz, 1H), 4.38 (t, J = 4.0 Hz, 2H), 4.15-4.14 (m, 6H), 3.86-3.47 (m, 16H), 2.33 (s, 3H), 2.32 (s, 3H); ESI ψι/ζ) [Qe^NOnSz + H]+ 642. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | Stage #1: D-Mannose; S,S'-((4-(2-aminoethoxy)-1,2-phenylene)bis(methylene)) bis(2-methylpropanethioate) hydrochloride With sodium cyanoborohydride; acetic acid In methanol at 55℃; for 7h; Stage #2: With hydrogenchloride In water | 30 30. Preparation oiSJS'-((4-(2-(bis((2R,3R,4R,SR)-2,3,4,S,6- pentahydroxyhexyl)amino)ethoxy)-l,2-phenylene)bis(methylene)) bis(2- methylpropanethioate) hydrochloride (75) A soluiion of amine 48 (1.00 g, 2.46 mmol) in methanol (40 mL) was charged with D- mannose (886 mg, 4.92 mmol) and acetic acid (295 mg, 4.92 mmol) successively followed by sodium cyanoborohydride (307 mg, 4,92 mmol) and the resulting reaction mixture was stirred at 55 °C for 2 h. Additional D-mannose (433 mg, 2.46 mmol), acetic acid (147 mg, 2.46 mmol) and sodium cyanoborohydride (153 mg, 2.46 mmol) were added and continued to be stirred at 55 °C for 2 h. Additional D-mannose (433 mg, 2.46 mmol), acetic acid (147 mg, 2.46 mmol) and sodium cyanoborohydride (153 mg, 2.46 mmol) were added and continued to be stirred at 55 °C for 2 h. Additional D-mannose (216 mg, 1.23 mmol), acetic acid (73 mg, 1.23 mmol) and sodium cyanoborohydride (76 mg, 1.23 mmol) were added and continued to be stirred at 55 °C for 1 h. Water (10 mL) was added and the resulting precipitated yellow solid was collected by filtration, to afford 1.50 g of compound 39 with 90% purity as free base. The solid acidified with 1 N HCl, to make HCl salt solution and purified by reverse-phase cliromaiography, to afford compound 75 (1.19 g, 66%) as an off-white solid: FontWeight="Bold" FontSize="10" H NMR (400 MHz, CD3OD) δ 7.24 (d, J = 8.4 Hz, 1H), 6.98 (d, J = 2.4 Hz, 1H), 6.88 (dd, J = 8.4, 2.4 Hz, 1H), 4.38 (br s, 2H), 4.14-4.12 (m, 6H), 3.82-3.30 (m, 16H), 2.77-2.72 (m, 2H), 1.18 (d, ./ 5.6 Hz, 6H), 1.16 (d, J = 5.6 Hz, 6H); ESI (m/z) [ C ,,, ;N(), ,S: + H]+ 698. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
33% | Stage #1: D-Mannose; S,S'-((4-(2-aminoethoxy)-1,2-phenylene)bis(methylene)) dipropanethioate hydrochloride With sodium cyanoborohydride; acetic acid In methanol at 55℃; for 8h; Stage #2: With hydrogenchloride In water | 44 44. Preparation of S,S '-((4- is((2R,3R,4R, 5R)-2,3,4, 5, 6- pentahydroxyhexyi)amino l,2-phenylene)bis(methylene)) dipropanethioate hydrochloride (89) A solution of amine 50 (800 mg, 2.1 1 mmol) in methanol (50 mL) was charged with D- mannose (1.14 g, 6.35 mmol) and acetic acid (381 mg, 6.35 mmol) successively followed by sodium cyanoborohydride (398 mg, 6.35 mmol) and the resulting reaction mixture was stirred at 55 °C for 3 h. Additional D-mannose (1.14 g, 6.35 mmol), acetic acid (381 mg, 6.35 mmol) and sodium cyanoborohydride (398 mg, 6.35 mmol) were added and continued to be stirred at 55 °C for 3 h. Additional D-mannose (1.14 g, 6.35 mmol), acetic acid (381 mg, 6.35 mmol) and sodium cyanoborohydride (398 mg, 6,35 mmol) were added and continued to be stirred at 55 °C for 2 h. Water (12.5 mL) was added and the resulting mixture was kept in fridge for 4 h. The precipitated solid was collected by filtration, to afford 1.14 g of compound 89 with 95% purity as free base. The solid acidified with 1 N HCI, to make HCI salt solution and purified by reverse-phase chromatography, to afford compound 53 (495 mg, 33%) as an off-white solid: M l NMR (400 MHz, CD3OD) δ 7.25 (d, J = 8.4 Hz, 1 1 ). 6.99 id. J 2.8 Hz, i l l ), 6.89 (dd, J = 8.4, 2.8 Hz, 1H), 4.37 (t, J = 4.0 Hz, 2H), 4.16-4.14 (m, 6H), 3.86-3.47 (m, 16H), 2.63-2.56 (m, 4H), 1.18-1.13 (m, 6H): ESI (m/z) [C28H47NO13S2 + H]+ 670. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With sodium cyanoborohydride; acetic acid In methanol at 50℃; for 8h; | 51 Preparation of S,'-((4~(2-(bi((2R,3R,4R,5R)~2,3,4,5,6~ pentahydroxyhexyl)amino)ethoxy)-l,2-phenylene)bis(methylene)) bis(furan-2- carbothioate) hydrochloride (102) A solution of amine 52 (1.00 g, 2.20 mmol) in methanol (40 mL) was charged with D- mannose (1 .60 g, 8.80 mmol) and acetic acid (0.50 mL, 8.80 mmol) successively followed by sodium cyanoborohydride (556 mg, 8.80 mmol) and the resulting reaction mixture was heated 50 °C and stirred at 50 °C for 6 h. Additional, D-mannose (1.0 equiv) and acetic acid (1.0 equiv) successively followed by sodium cyanoborohydride (1.0 equiv) and the resulting reaction mixture was heated stirred at 50 °C for another I h. Further additional, D-mannose (1.0 equiv) and acetic acid (1.0 equiv) successively followed by sodium cyanoborohydride (1.0 equiv) and the resulting reaction mixture was heated stirred at 50 °C for another 1 h. Reaction mixture was cooled to rt and water was added; after solvent was removed under reduced pressure, more water was added then solid precipitation came out which was filtered through filter paper and washed with water/methanol to get free base of the boron complex of 102 (1.10 g, 67%). 600 mg of free base of the born complex 102 was then acidified with 4 N HC1 in water to make HCL salt and lyophilized to get 102 (620 mg,) as an off-white solid. ]H NMR (400 MHz, CD3OD) δ 7.76-7.74 (m, 2H), 7.34 (d, J = 8.6 Hz, IH), 7.26 (ddd, J = 8.9, 3.5, 0.7 Hz, 2H), 7.10 (d, J = 2.6 Hz, IH), 6.93 (dd, J = 8.8, 2.9 Hz, IH), 6.63 (td, J = 3.8, 1.6 Hz, 2H), 4.42-4.36 (m, 2H), 4.38 (s, 2H), 4.36 (s, 2H), 4.19-4.07 (m, 2H), 3.90- 3.61 (m, 14H), 3.53-3.42 (m, 2H); NMR (400 MHz, DMSO-i/6) δ 8.04-8.00 (m, 2H), 7.40 (dd, J = 9.8, 3.8, 0.7 Hz, 2H), 7.35 (d, J = 9.0 Hz, I H), 7.06-7.01 (m, I H), 6.96-6.98 (m, IH), 6.76 (td, J = 4.1, 1.7 Hz, 2H), 4.37 (s, 2H), 4.35 (s, 2H), 4.34-3.87 (m, 15H), 3.79-3.17 (m, 16H); ESI MS m/z 746 |( ;:Η , FontWeight="Bold" FontSize="10" Ν()·. ,82 + H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.11% | With citric acid In methanol for 7h; Reflux; | 2 Example 2 1-L-leucine-1-deoxy-D-fructose,Which comprises the following steps: Weigh D-mannose 0.06 mils In a 500 mL three-necked flask, 240 mL of anhydrous methanol was added, the mixture was stirred under magnetic stirring for 40 min, followed by the addition of 0.072 mol leucine and 0.0024 mol of citric acid followed by a reflux reaction for 7 h reaction. After the reaction solution was cooled to room temperature, the unreacted D-mannose and the amino acid were filtered off, and then concentrated under reduced pressure,The residue was separated and recrystallized by sub-exchange resin column chromatography to give 14.964 g of product as a white product in 68.11% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With acetic acid In ethanol for 6h; Reflux; | 5.2.9. General procedure for the preparation of 6-(5-(4-Fluorophenyl)-4-((Z)-((2S,3R,4S)-2,3,4,5-tetrahydroxypentylidene)/((2S,3S,4S,5S)-2,3,4,5,6-pentahydroxyhexylidene) amino)pyrido[2,3-d]pyrimidin-7-yl)-4,9-dimethoxy-7-methyl-5H-furo[3,2-g]chromen-5-one XVa,b General procedure: A mixture of the compound XIV (5 g, 10 mmol) and the appropriate linear sugar namely: D-ribose and D-mannose (10 mmol) inabsolute ethanol in the presence of few drops of glacial acetic acidwas refluxed for 6 h. The reaction mixture was cooled and the formed precipitate was filtered and recrystallized from isopropanol/water to obtain the desired C-nucleosides XVa,b,respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With acetic acid; In ethanol; for 10.0h;Reflux; | General procedure: To solution of 4 (10 mmol) in absolute ethanol, different sugars (10 mmol) were added and then glacial acetic acid (1 ml) was added to the reaction mixture which was refluxed for 10h (TLC).The solvent was evaporated or concentrated under reduced pressure and the product was filtered off to afford 5(a-d) (83 - 88%) yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With hydrogenchloride In ethanol; water for 6h; Reflux; | Synthesis of aldose N-(1,3-diphenylpyrazolo[3,4-d]pyrimidin-4-yl)-hydrazones (3a-f); general procedure General procedure: One drop of hydrochloric acid (6M) was added to a mixture of4-hydrazino-1,3-diphenylpyrazolo[3,4-d]pyrimidine 1 (0.6 g, 2 mmol)and the appropriate sugar aldehyde 2a-f (2 mmol) in ethanol (25 mL).The reaction mixture was refluxed for 6 h, then cooled and precipitatedby adding water. The precipitate formed was filtered off, washed withwater, ethanol and finally crystallised from the appropriate solvent togive the corresponding hydrazone derivative 3a-f. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27.21% | With 1,3-dimethyl-2-imidazolidinone; carbon dioxide; dihydrogen peroxide; oxygen; carbonic acid dimethyl ester at 185℃; for 0.166667h; Autoclave; Green chemistry; | 6 A one-step cleaning method for preparing 2,5-furandicarboxylic acid includes the following steps: 20 g of mannose, 0.5 g of sodium carbonate-zinc glutarate in a mass ratio of 3: 1, 0.45 g of a ruthenium-based lanthanum niobic acid catalyst, and 100 g of hydrogen peroxide in a volume ratio of 1: 1: 18,A mixed solvent composed of 1,3-dimethyl-2-imidazolinone solution and dimethyl carbonate was poured into a high-pressure reaction kettle, quickly sealed, and stirred uniformly at a speed of 300 r / min.Pass in a CO2 / O2 mixed gas with a volume ratio of 1: 2.5 until the pressure in the autoclave is 6 MPa, then heat it to 185 ° C, and stop the reaction after 10 minutes of reaction.1 mL of the reaction solution was taken from the sampling tube and the product was analyzed by high performance liquid chromatography. The following results were obtained: the conversion of mannose was 85.45%, and the yield of 2,5-furandicarboxylic acid was 27.21%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sulfuric acid at 0 - 20℃; for 24h; | 1.a.1 Step a1. Preparation of (3aR,4R,6R,6aR)-6-(2,2-dimethyl-1,3-dioxolane-4-yl)-2,2-dimethyl-tetrahydrofuro[3,4-d] [1,3]dioxol-4-ol D-mannose (1.74 g, 6.52 mmol) and 2,2-dimethoxypropane (2.45 ml, 19.55 mmol) were added to acetone (50 ml), stirred and cooled to 0° C. Concentrated sulfuric acid (0.45 g, 1.96 mmol) was added dropwise to it. The reaction mixture was stirred at room temperature for 24 hours. Triethylamine was added to the mixture for neutralization, and the mixture was concentrated under reduced pressure. The mixture obtained after concentration was subjected to silica gel column chromatography using a hexane:ethyl acetate mixed solvent (1:1, v/v) as an eluent to obtain the target compound as a white solid (1.61 g, 95%). (0127) mp 120.3-120.5° C.; (0128) 1H-NMR (CDCl3) δ 5.34 (s, 1H), 4.76-4.79 (m, 1H), 4.58 (d, 1H, J=6.0 Hz), 4.34-4.39 (m, 1H), 4.15 (dd, 1H, J=3.6, 7.2 Hz), 4.00-4.08 (m, 2H); (0129) [α]25D 11.71 (c 0.11, CH2Cl2); (0130) FAB-MS m/z 261 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With phenoxyamine hydrochloride In aq. phosphate buffer; water-d2 at 20℃; for 24h; | 1.1.3 General procedure for the formation of cyanohydrins General procedure: To a 7mL vial was added reducing sugar (1 equiv), O-phenylhydroxylamine hydrochloride (H2NOPh) (1.2 equiv), and 0.2M sodium phosphate pD 7.25 to the final concentration of 0.1M. The reaction was stirred at room temperature until the oxime intermediates were disappeared (monitored by 1H NMR). Then, the reaction mixture was transferred into a separatory funnel and washed with diethyl ether for 10 times. The remaining aqueous solution was evaporated to dryness. Ethanol was added to the solid residue to extract the product from the phosphate salt. The phosphate salt residues in the ethanol solution were removed by centrifugation. The solvent was evaporated to obtain the desired product. |
Yield | Reaction Conditions | Operation in experiment |
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With recombinant GH68 β-fructofuranosidase In aq. acetate buffer at 35℃; for 6h; Enzymatic reaction; | Production of 6-kestose and Fru-Man This research required the preparation of an appropriateamount of standard 6-kestose. For this, we did the 10 mllevelreaction of 37 U mL-1 H79N/A343S-FFZm with1.0 M sucrose at 35 C and pH 5.0 for 2 h. Reaction solutionwas desalted by Amberlite MB-4 resin (Organo), and thenconcentrated to 2 ml under reduced pressure. The reactionproducts were separated by an HPLC system (Jasco) equippedwith a refractive index monitor (Jasco RI-2031) with aCosmosil Sugar-D column (10 mm I.D. × 250 mm; NacalaiTesque). Separation was achieved using a mobile phase(acetonitrile:water, 80:20, v/v) with a flow rate of 3 ml min-1.For Fru-Man synthesis, 1.25 M sucrose and 2.5 M mannosewith 25 U mL-1 FFZm in 10 ml of 40 mM sodium acetatebuffer were incubated at 35 C for 6 h. The reaction mixturewas divided into three equal parts and was fractionated bygel filtration chromatography using Bio-Gel P-2 Gel (1.6 cmI.D. × 190 cm, Bio-Rad). Fractions containing Fru-Man wererecovered and concentrated under reduced pressure.Reducing sugars were decomposed by the incubation with2 M NaOH at 100 C for 10 min. The reaction solution wasneutralized by adding Amberlite IR120 H+ form and decolorizedby activated carbon. The resulting samples were againsubjected to gel filtration chromatography and purified Fru-Man was obtained |
Tags: 3458-28-4 synthesis path| 3458-28-4 SDS| 3458-28-4 COA| 3458-28-4 purity| 3458-28-4 application| 3458-28-4 NMR| 3458-28-4 COA| 3458-28-4 structure
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Code | Phrase |
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Response | |
Code | Phrase |
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P378 | |
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Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
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Disposal | |
Code | Phrase |
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Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
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H223 | Flammable aerosol |
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H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
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H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
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H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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