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CAS No. : | 141-46-8 | MDL No. : | MFCD00038088 |
Formula : | C2H4O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | WGCNASOHLSPBMP-UHFFFAOYSA-N |
M.W : | 60.05 | Pubchem ID : | 756 |
Synonyms : |
|
Num. heavy atoms : | 4 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.5 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 13.09 |
TPSA : | 37.3 Ų |
GI absorption : | High |
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) : | -7.33 cm/s |
Log Po/w (iLOGP) : | 0.29 |
Log Po/w (XLOGP3) : | -0.93 |
Log Po/w (WLOGP) : | -0.82 |
Log Po/w (MLOGP) : | -1.3 |
Log Po/w (SILICOS-IT) : | -0.33 |
Consensus Log Po/w : | -0.62 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | 0.44 |
Solubility : | 165.0 mg/ml ; 2.75 mol/l |
Class : | Highly soluble |
Log S (Ali) : | 0.63 |
Solubility : | 257.0 mg/ml ; 4.27 mol/l |
Class : | Highly soluble |
Log S (SILICOS-IT) : | 0.52 |
Solubility : | 197.0 mg/ml ; 3.28 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Danger | Class: | 3 |
Precautionary Statements: | P501-P240-P210-P233-P243-P241-P242-P264-P280-P370+P378-P337+P313-P305+P351+P338-P362+P364-P303+P361+P353-P332+P313-P403+P235 | UN#: | 1993 |
Hazard Statements: | H315-H319-H225 | Packing Group: | Ⅲ |
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 |
---|---|---|
71.3% | With sodium hydroxide In tetrahydrofuran; water at 0 - 20℃; for 24 h; | Example 2: Preparation of 2-amino-oxazole. To a solution of cyanamide (19.8 ml of 50percent w/w in water, 0.25 mol) in THF (60 ml) was added the hydroxyacetaldehyde (15 g, 0.25 mol) in 24 ml of water. The reaction mixture was treated at 00C with a solution of sodium hydroxide 2 M (25.2 ml, 0.05 mol). The mixture was allowed to warm to room temperature and stirred for 24 hrs. The volatiles were removed in vacuo (THF) and the remaining aqueous solution was extracted with four portions of 200 ml of ethyl acetate. The organic extracts were dried over sodium sulfate and concentrated in vacuo, yielding 14.968 g (71.3percent) of a white solid. 400 MHz 1H NMR (CDCl3) δ: 7.13 (s, IH), 6.74 (s, IH), 5.26 (br. s, 2H). CaIc. for C3H4N2O: C 42.86, H 4.80, N 33.32; found C 43.01, H 4.87, N 33.11. |
66% | With sodium hydroxide In tetrahydrofuran; water at 0℃; for 24 h; | To a solution of cyanamide (33ml, 50percentwt in water, 0.416mol) in THF (100ml), wasadded an aqueous solution of 2-hydroxyacetaldehyde (25g, 0.41 6mol) in water (40ml),followed by the dropwise addition of 2M sodium hydroxide (42ml, 0.083mol) at 0°C. Stirringwas continued for a total of 24 hours. Then, the reaction mixture was concentrated in vacua toremove most of the THF. The remaining water layer was extracted with ethyl acetate (4 x200ml). The extract was dried over sodium sulfate and the solvent was evaporated in vacua.This gave the white solid product A (23 g, 66percent). |
66% | With sodium hydroxide In tetrahydrofuran; water at 0℃; for 24 h; | Example 35: Preparation of 2-amino-oxazole.; To a solution of cyanamide (33 ml, 50percent wt in water, 0.416 mol) in THF (100 ml), is added an aqueous solution of 2-hydroxyacetaldehyde (25g, 0.416 mol) in water (40ml),followed by the dropwise addition of 2M sodium hydroxide (42 ml, 0.083 mol) at O°C.Stirring is continued for a total of 24 hours. Then, the reaction mixture is concentrated in vacuo to remove most of the THF. The remaining water layer is extracted four times with 200 ml each of ethyl acetate. The extract is dried over sodium sulfate and the solvent is evaporated in vacuo. This produces a white solid product (23g, 66percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.3% | In water at 500℃; for 5.64h; | 1A; 1B; 1C; 1D; 1E; 2 General procedure: A bed mass of 100 g was loaded in a bubbling fluid bed reactor (42 mm ID) and fluid ized at a superficial gas velocity of approx. 30 cm/s. The temperature was increased to 500°C, at which point water was injected into the bed through a two-fluid nozzle at a rate of 2 g/min. Once the system reached steady state, the feed was switched to a 10 wt.% aqueous solution of glucose and time set as to. The gas leaving the reactor was cooled to 1°C in a surface condenser, and the liquid condensate collected. The con centration of oxygenates in the condensate was determined by HPLC analysis, and the yield of oxygenates calculated based on the mass of collected product. |
With water; magnesium carbonate | ||
With water; calcium carbonate |
With oxygen In water at 180℃; for 1h; Autoclave; | ||
With sodium borate; molybdenum(VI) oxide In methanol at 170℃; for 0.0166667h; | ||
With molybdenum(VI) oxide In ethanol at 190℃; for 2.66667h; | ||
With vanadium oxide-coated glass bead at 525℃; for 50h; Pyrolysis; Flow reactor; | 7 Example 3: Pyrolysis of Dextrose Utilizing a Glass Bead Catalyst General procedure: Untreated glass bead catalysts were tested for pyrolysis of dextrose utilizing a fluidized bed reactor system. The glass bead catalysts represented 6% of the total media volume of the reactor bed. An approximately 20 wt.% dextrose solution was introduced into the reactor system at a rate of 1.7 mL/min. A nitrogen gas stream was also directed into the system at a rate of 4500-5000 mL/min. Tables 1-3, below, report the product profile at various time on stream for differing reaction temperatures. Each of the reactions set forth below had a 0.98 s residence time | |
With molybdenum oxide-coated glass bead at 525℃; for 50h; Pyrolysis; Flow reactor; | 7 Example 3: Pyrolysis of Dextrose Utilizing a Glass Bead Catalyst General procedure: Untreated glass bead catalysts were tested for pyrolysis of dextrose utilizing a fluidized bed reactor system. The glass bead catalysts represented 6% of the total media volume of the reactor bed. An approximately 20 wt.% dextrose solution was introduced into the reactor system at a rate of 1.7 mL/min. A nitrogen gas stream was also directed into the system at a rate of 4500-5000 mL/min. Tables 1-3, below, report the product profile at various time on stream for differing reaction temperatures. Each of the reactions set forth below had a 0.98 s residence time |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride | ||
With S2O82-/silicon MCM-41 at 100℃; for 3h; | 2.1; 3.1; 4.1; 5.1 [Example 2] 1) Add 600g (10mol) of hydroxyacetaldehyde and 20mol of methanol into the reactor,Then add 12g of the S2O82-/MCM-41 catalyst prepared in Example 1,Warm up to 100°C,React for 10 hours. After the reaction is over, cool down and recover methanol under reduced pressure.Distillation to obtain the product 2,2-dimethoxyethanol; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium chlorite; dimethyl sulfoxide; In aq. phosphate buffer; at 0 - 20℃;pH 4.0; | General procedure: Aldehyde (70-350 mM), an internal standard (DSS or 20) and the specified additive (none, NH4Cl, H2O2, DMS, DMSO, sulfamic acid or L-methinone) were dissolved in phosphate buffer (60 mM, D2O, pH 4-7). Sodium chlorite (5 M, 1.4 equiv.) was added in five portions over 1 h at 0 C, then the solution was warmed to ambient temperature and NMR spectra were acquired. The carboxylic acid product was confirmed by sample spiking, and the yield (Table 1 and Supplementary Table 1) was quantified with respect to the internal standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ethanol; hydrogen cyanide; ammonia man fuegt waessr.Salzsaeure hinzu und engt die filtrierte Fluessigkeit ein; | ||
With ammonium hydroxide; sodium hydroxide; ammonium chloride In water | 1 EXAMPLE 1 EXAMPLE 1 Into a 50-ml three-necked flask equipped with a thermometer and a cooling pipe were charged 1.32 g (22.0 mmole) of glycol aldehyde, 0.98 g (20 mmole) of sodium cyanide, 1.29 g (24.2 mmole) of ammonium chloride, 6.8 g (100 mmole) of 25% aqueous ammonia and 7.5 g of water as the solvent, and the reaction was carried out at 60.C for 30 minutes. Then, to carry out the hydrolysis reaction, an aqueous sodium hydroxide solution containing 2.2 g (55 mmole) of sodium hydroxide dissolved in 15 g of water was added into the Strecker reaction mixture, and the reaction was carried out at 75° C. for 4 hours. After completion of the reaction, DL-serine was quantitated by liquid chromatography. As the result, the amount of DL-serine produced was 1.94 g and that of glycine as by-product 0.0075 g. The yields as calculated on the basis of sodium cyanide were found to be 92.2% of the theoretical amount for DL-serine, and 0.5% of the theoretical amount for glycine of the by-product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.3% | With sodium hydroxide; In tetrahydrofuran; water; at 0 - 20℃; for 24h; | Example 2: Preparation of 2-amino-oxazole. To a solution of cyanamide (19.8 ml of 50% w/w in water, 0.25 mol) in THF (60 ml) was added the hydroxyacetaldehyde (15 g, 0.25 mol) in 24 ml of water. The reaction mixture was treated at 00C with a solution of sodium hydroxide 2 M (25.2 ml, 0.05 mol). The mixture was allowed to warm to room temperature and stirred for 24 hrs. The volatiles were removed in vacuo (THF) and the remaining aqueous solution was extracted with four portions of 200 ml of ethyl acetate. The organic extracts were dried over sodium sulfate and concentrated in vacuo, yielding 14.968 g (71.3%) of a white solid. 400 MHz 1H NMR (CDCl3) delta: 7.13 (s, IH), 6.74 (s, IH), 5.26 (br. s, 2H). CaIc. for C3H4N2O: C 42.86, H 4.80, N 33.32; found C 43.01, H 4.87, N 33.11. |
66% | With sodium hydroxide; In tetrahydrofuran; water; at 0℃; for 24h; | To a solution of cyanamide (33ml, 50%wt in water, 0.416mol) in THF (100ml), wasadded an aqueous solution of 2-hydroxyacetaldehyde (25g, 0.41 6mol) in water (40ml),followed by the dropwise addition of 2M sodium hydroxide (42ml, 0.083mol) at 0C. Stirringwas continued for a total of 24 hours. Then, the reaction mixture was concentrated in vacua toremove most of the THF. The remaining water layer was extracted with ethyl acetate (4 x200ml). The extract was dried over sodium sulfate and the solvent was evaporated in vacua.This gave the white solid product A (23 g, 66%). |
66% | With sodium hydroxide; In tetrahydrofuran; water; at 0℃; for 24h; | Example 35: Preparation of 2-amino-oxazole.; To a solution of cyanamide (33 ml, 50% wt in water, 0.416 mol) in THF (100 ml), is added an aqueous solution of 2-hydroxyacetaldehyde (25g, 0.416 mol) in water (40ml),followed by the dropwise addition of 2M sodium hydroxide (42 ml, 0.083 mol) at OC.Stirring is continued for a total of 24 hours. Then, the reaction mixture is concentrated in vacuo to remove most of the THF. The remaining water layer is extracted four times with 200 ml each of ethyl acetate. The extract is dried over sodium sulfate and the solvent is evaporated in vacuo. This produces a white solid product (23g, 66%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In ethanol Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 63.52% 2: 23.12% | With triethylamine In N,N-dimethyl-formamide at 120℃; for 1h; | 43 Formaldehyde (30 mmol) was placed in a reaction kettle, and then N,N-dimethylformamide (10 ml) was added to the reaction vessel.Add ruthenium catalyst I-K (0.15 mmol, as shown in Figure 2) or silica-supported triazole catalyst A-H(1g, 0.15mmol triazole salt / g carrier, as shown in Figure 2),Additive triethylamine (0.70 mmol).The reaction vessel was installed, and the reaction was stirred at a temperature of 0 to 300 ° C and a pressure of 0 to 10 MPa for 1 to 1000 minutes.After completion of the reaction, the produced glycolaldehyde and glyceraldehyde were detected by liquid chromatography, and the results are shown in Table 1. |
1: 38.23% 2: 25.17% | With triethylamine In N,N-dimethyl-formamide at 100℃; for 1h; | 5 Formaldehyde (30 mmol) was placed in a reaction kettle, and then N,N-dimethylformamide (10 ml) was added to the reaction vessel.Add ruthenium catalyst I-K (0.15 mmol, as shown in Figure 2) or silica-supported triazole catalyst A-H(1g, 0.15mmol triazole salt / g carrier, as shown in Figure 2),Additive triethylamine (0.70 mmol).The reaction vessel was installed, and the reaction was stirred at a temperature of 0 to 300 ° C and a pressure of 0 to 10 MPa for 1 to 1000 minutes.After completion of the reaction, the produced glycolaldehyde and glyceraldehyde were detected by liquid chromatography, and the results are shown in Table 1. |
With 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2-4-triazoline In various solvent(s) at 80℃; |
1: 6 - 39 %Chromat. 2: 2 - 34 %Chromat. | With triethylamine In N,N-dimethyl-formamide at 60 - 100℃; for 0.416667 - 4h; | 1; 2; 3; 4; 5; 6; 7 A MulitiMax reaction flask equipped with a stir bar and a reflux condenser was charged with 1.0 g (33.0 mmol) of paraformaldehyde and 0.070 g (0.16 mmol, 0.5 mol %) of 1,3-bis(2,6-di-i-propylphenyl)imidazolium chloride. The flask was assembled and purged with nitrogen. Under positive nitrogen flow 40.0 mL of N,N-dimethylformamide and 0.092 mL (0.64 mmol) triethylamine were added. The reaction mixture was heated at 100° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.32 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC and contained 27% of glycolaldehyde, 6% of glyceraldehyde and 67% of formaldehyde. Selectivity of glycolaldehyde in solution is 82%.Example 2Procedure was followed as in Example 1 except that the reaction mixture was heated at 80° C. for 4 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.18 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 19% of glycolaldehyde, 34% of glyceraldehyde and 47% of formaldehyde. Selectivity of glycolaldehyde in solution is 36%.Example 3Procedure was followed as in Example 1 except that 0.28 g (0.66 mmol, 2.0 mol %) of 1,3-bis(2,6-di-i-propylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 80° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.16 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 30% of glycolaldehyde, 28% of glyceraldehyde and 42% of formaldehyde. Selectivity of glycolaldehyde in solution is 52%.Example 4Procedure was followed as in Example 1 except that the reaction mixture was heated at 80° C. for 25 min. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.60 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 14% of glycolaldehyde, 2% of glyceraldehyde and 84% of formaldehyde. Selectivity of glycolaldehyde in solution is 88%.Example 5Procedure was followed as in Example 1 except that 0.28 g (0.66 mmol, 2.0 mol %) of 1,3-bis(2,6-di-i-propylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 80° C. for 25 min. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.37 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 22% of glycolaldehyde, 9% of glyceraldehyde and 69% of formaldehyde. Selectivity of glycolaldehyde in solution is 71%.Example 6Procedure was followed as in Example 1 except that the reaction mixture was heated at 60° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.73 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 17% of glycolaldehyde, 2.5% of glyceraldehyde and 80.5% of formaldehyde. Selectivity of glycolaldehyde in solution is 87%.Example 7Procedure was followed as in Example 1 except that 0.28 g (0.66 mmol, 2.0 mol %) of 1,3-bis(2,6-di-i-propylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 60° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.10 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 39% of glycolaldehyde, 13% of glyceraldehyde and 48% of formaldehyde. Selectivity of glycolaldehyde in solution is 75%. |
1: 10 - 20 %Chromat. 2: 5 - 45 %Chromat. | With triethylamine In N,N-dimethyl-formamide at 60 - 80℃; for 0.416667 - 4h; | 12; 13; 14; 15; 16; 17; 18; 19; 20; 21 Example 1; A MulitiMax reaction flask equipped with a stir bar and a reflux condenser was charged with 1.0 g (33.0 mmol) of paraformaldehyde and 0.070 g (0.16 mmol, 0.5 mol %) of 1,3-bis(2,6-di-i-propylphenyl)imidazolium chloride. The flask was assembled and purged with nitrogen. Under positive nitrogen flow 40.0 mL of N,N-dimethylformamide and 0.092 mL (0.64 mmol) triethylamine were added. The reaction mixture was heated at 100° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.32 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC and contained 27% of glycolaldehyde, 6% of glyceraldehyde and 67% of formaldehyde. Selectivity of glycolaldehyde in solution is 82%.; Example 12; Procedure was followed as in Example 1 except that 0.22 g (0.66 mmol, 2.0 mol %) of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 80° C. for 25 min. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.21 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 16% glycolaldehyde, 5% glyceraldehyde and 79% formaldehyde. Selectivity to glycolaldehyde in solution is 76%.; Example 13; Procedure was followed as in Example 12 except that 0.056 g (0.165 mmol, 0.5 mol %) of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 80° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.22 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 11% of glycolaldehyde, 5% of glyceraldehyde and 84% of formaldehyde. Selectivity of glycolaldehyde in solution is 69%.; Example 14; Procedure was followed as in Example 12 except that the reaction mixture was heated at 80° C. for 4 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.18 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 16% of glycolaldehyde, 25% of glyceraldehyde and 59% of formaldehyde. Selectivity of glycolaldehyde in solution is 39%.; Example 15; Procedure was followed as in Example 12 except that the reaction mixture was heated at 80° C. for 25 min. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.16 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 20% of glycolaldehyde, 24% of glyceraldehyde and 56% of formaldehyde. Selectivity of glycolaldehyde in solution is 45%.; Example 16; Procedure was followed as in Example 12 except that the reaction mixture was heated at 80° C. for 4 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.16 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 15% of glycolaldehyde, 45% of glyceraldehyde and 40% of formaldehyde. Selectivity of glycolaldehyde in solution is 25%.; Example 17; Procedure was followed as in Example 12 except that 0.56 g (1.65 mmol, 5.0 mol %) of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 80° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.26 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 17% of glycolaldehyde, 17% of glyceraldehyde and 66% of formaldehyde. Selectivity of glycolaldehyde in solution is 50%.; Example 18; Procedure was followed as in Example 1 except that 0.056 g (0.16 mmol, 0.5 mol %) of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 80° C. for 25 min. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.54 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 10% of glycolaldehyde, 1.5% of glyceraldehyde and 88.5% of formaldehyde. Selectivity of glycolaldehyde in solution is 87%.; Example 19; Procedure was followed as in Example 12 except that the reaction mixture was heated at 60° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.54 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 15% of glycolaldehyde, 5% of glyceraldehyde and 80% of formaldehyde. Selectivity of glycolaldehyde in solution is 75%.; Example 20; Procedure was followed as in Example 12 except that 0.56 g (1.65 mmol, 5.0 mol %) of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 60° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.32 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 16% of glycolaldehyde, 10% of glyceraldehyde and 74% of formaldehyde. Selectivity of glycolaldehyde in solution is 62%.; Example 21; Procedure was followed as in Example 12 except that the reaction mixture was heated at 60° C. for 4 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.18 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 13.5% of glycolaldehyde, 12% of glyceraldehyde and 74.5% of formaldehyde. Selectivity of glycolaldehyde in solution is 53%. |
1: 38 - 44 %Chromat. 2: 4 - 8 %Chromat. | With triethylamine In tetrahydrofuran at 80℃; for 1h; | 22; 23 Procedure was followed as in Example 12 except that 0.056 g (0.16 mmol, 0.5 mol %) of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride catalyst was used. The reaction mixture was heated at 80° C. for 1 h in 40.0 mL of THF. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.54 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 38% of glycolaldehyde, 4% of glyceraldehyde and 58% of formaldehyde. Selectivity of glycolaldehyde in solution is 91%.Example 23Procedure was followed as in Example 12 except that the reaction mixture was heated at 80° C. for 1 h in 40.0 mL of THF. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.42 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 44% of glycolaldehyde, 8% of glyceraldehyde and 48% of formaldehyde. Selectivity of glycolaldehyde in solution is 85%. |
1: 55 %Chromat. 2: 18 %Chromat. | With triethylamine In ethyl acetate at 80℃; for 1h; | 11 A MulitiMax reaction flask equipped with a stir bar and a reflux condenser was charged with 1.0 g (33.0 mmol) of paraformaldehyde and 0.070 g (0.16 mmol, 0.5 mol %) of 1,3-bis(2,6-di-i-propylphenyl)imidazolium chloride. The flask was assembled and purged with nitrogen. Under positive nitrogen flow 40.0 mL of N,N-dimethylformamide and 0.092 mL (0.64 mmol) triethylamine were added. The reaction mixture was heated at 100° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.32 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC and contained 27% of glycolaldehyde, 6% of glyceraldehyde and 67% of formaldehyde. Selectivity of glycolaldehyde in solution is 82%.; Example 11; Procedure was followed as in Example 1 except that the reaction mixture was heated at 80° C. for 1 h in 40.0 mL of EtOAc. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.46 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 55% of glycolaldehyde, 18% of glyceraldehyde and 27% of formaldehyde. Selectivity of glycolaldehyde in solution is 75%. |
1: 46 - 61 %Chromat. 2: 2 - 7.5 %Chromat. | With triethylamine In tetrahydrofuran at 60 - 80℃; for 1h; | 8; 9; 10 A MulitiMax reaction flask equipped with a stir bar and a reflux condenser was charged with 1.0 g (33.0 mmol) of paraformaldehyde and 0.070 g (0.16 mmol, 0.5 mol %) of 1,3-bis(2,6-di-i-propylphenyl)imidazolium chloride. The flask was assembled and purged with nitrogen. Under positive nitrogen flow 40.0 mL of N,N-dimethylformamide and 0.092 mL (0.64 mmol) triethylamine were added. The reaction mixture was heated at 100° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.32 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC and contained 27% of glycolaldehyde, 6% of glyceraldehyde and 67% of formaldehyde. Selectivity of glycolaldehyde in solution is 82%.; Example 8; Procedure was followed as in Example 1 except that 40.0 mL of THF were used as the solvent. The reaction mixture was heated at 80° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.43 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 46% of glycolaldehyde, 6% of glyceraldehyde and 48% of formaldehyde. Selectivity of glycolaldehyde in solution is 89%.; Example 9; Procedure was followed as in Example 1 except that the reaction mixture was heated at 60° C. for 1 h and THF was used as the solvent. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.85 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 52% of glycolaldehyde, 2% of glyceraldehyde and 46% of formaldehyde. Selectivity of glycolaldehyde in solution is 96%.; Example 10; Procedure was followed as in Example 1 except that 0.28 g (0.66 mmol, 2.0 mol %) of 1,3-bis(2,6-di-i-propylphenyl)imidazolium chloride catalyst was used and THF was used as the solvent. The reaction mixture was heated at 60° C. for 1 h in 40.0 mL of THF. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.73 g of unreacted dry paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 61% of glycolaldehyde, 7.5% of glyceraldehyde and 31.5% of formaldehyde. Selectivity of glycolaldehyde in solution is 89%. |
1: 46.5 %Chromat. 2: 3.5 %Chromat. | With triethylamine In ethyl acetate at 80℃; for 1h; | 25 A glass pressure vessel was charged with 1.0 g (33.0 mmol) of paraformaldehyde and 0.490 g (1.5 mmol, 4.5 mol %) of 1,3-bis(4-chlorophenyl)imidazolium chloride. To this was added 15.5 mol EtOAc and 232 μL (1.65 mmol) of Et3N. The reaction mixture was heated at 80° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 1.3 g of paraformaldehyde remained, still containing some solvent. The filtrate was analyzed by HPLC containing 46.5% of glycolaldehyde, 3.5% of glyceraldehyde and 50% of formaldehyde. Selectivity of glycolaldehyde in solution is 93%. |
1: 37 %Chromat. 2: 30 %Chromat. | With triethylamine In ethyl acetate at 80℃; for 1h; | 24 A glass pressure vessel was charged with 1.0 g (33.0 mmol) of paraformaldehyde and 0.656 g (1.65 mmol, 5.0 mol %) of 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium tetrafluoroborate. To this was added 15.5 mol EtOAc and 232 μL (1.65 mmol) of Et3N. The reaction mixture was heated at 80° C. for 1 h. At the end of the reaction, unreacted paraformaldehyde was removed by filtration and dried. 0.5 g of unreacted paraformaldehyde was recovered. The filtrate was analyzed by HPLC containing 37% of glycolaldehyde, 30% of glyceraldehyde and 33% of formaldehyde. Selectivity of glycolaldehyde in solution is 55%. |
1: 62 %Chromat. 2: 34 %Chromat. | With (1,3,4)-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene In N,N-dimethyl-formamide for 1h; Overall yield = 96 percentChromat.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Dissolve <strong>[147688-58-2]2,2-<strong>[147688-58-2]dimethylmorpholine</strong></strong> (151 mg, 1.0 rnmol) in 1,2-dichloroethane (3 mL) and add glycolaldehyde (60 mg, 1.0 mmol). Stir at room temperature for 30 min followed by addition of NaBH(OAc)3 (233 mg, 1.1 mmol). Stir 3 h, then quench by adding 30 mL of IN NaOH. Pour into a separatory funnel and extract with EtOAc (2 x 50 mL). Wash the combined organic layers with brine (50 mL). The crude alcohol was used as is without further purification. MS (ES+) 160.2 (M+ 1)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; | Example 1 A 0.05 molar solution of glycolaldehyde, a 0.05 molar solution of <strong>[2498-50-2]4-aminobenzamidine dihydrochloride</strong> and a 0.05 molar solution of N-[2-(1H-indol-3-yl)ethyl]-3-methylbutanamide-2-isonitrile in methanol was reacted for 24 hours at room temperature in a sealed vessel. After evaporation of the solvent the product was subjected to liquid chromatography and mass spectroscopy to verify the structural integrity of the final product. The product 2-[2-({3-[amino(imino)-methyl]phenyl}amino)-3-hydroxypropanoyl]amino}-N-[2-(1H-indol-3-yl)ethyl]-3-methylbutanamide hydrochloride can be purified with liquid chromatography and using a water-methanol gradient as eluent on a reversed phase chromatography column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In toluene; | a) Malononitrile (0.50 g, 7.6 mmol), glycol aldehyde (0.32 g, 2.7 mmol), and triethylamine (0.40 ml, 2.9 mmol) were suspended in toluene (8.7 ml) and the mixture was heated to reflux for 10 minutes. The reaction mixture was washed with brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 2-amino-3-cyanofuran (0.27 g, 2.5 mmol). | |
With triethylamine; In toluene; | a) Malononitrile (0.50 g, 7.6 mmol), glycol aldehyde (0.32 g, 2.7 mmol), and triethylamine (0.40 ml, 2.9 mmol) were suspended in toluene (8.7 ml) and the mixture was heated to reflux for 10 minutes. The reaction mixture was washed with brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 2-amino-3-cyanofuran (0.27 g, 2.5 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,4-dioxane at 70℃; for 2 - 5h; | 1.1.a 1.a. Transfer Hydrogenation Experiments; [075] In a typical experiment, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed out and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. Glycolaldehyde acetal and methylglycolate were obtained as the major by-products along with ethylene glycol. Yields of ethylene glycol ranging from 0-40% using RuCI2(PPh3)3, RuH2(PPh3)3, RuH2(PPh3)4, RuH(OAc)(PPh3)3, Ru(OAc)2(PPh3)3, Cp*lr(dpen)CI, Cp*Ru(OMe)2 and [Cp*lrCI2]2 were typically obtained. Substantial amounts of acetal were obtained primarily when RuCI2(PPh3)3, and particularly [Cp*lrCI2]2, were used. A typical chromatogram is shown in Figure 3 showing the production of ethylene glycol.[076] The transfer hydrogenation step was studied first in a separate set of experiments. Ethylene glycol was produced in varied yields. Under some experimental conditions, significant amounts of glycolaldehyde dimethylacetal and methyl glycolate were also formed as by-products. While acetal formation can be completely suppressed depending on the transition-metal complex used, formation of methyl glycolate is unavoidable and appears intrinsic to the overall process. Figure 4 provides a scheme showing the formation of methyl glycolate. The hydrogen produced in this transformation may be transferred by the metal catalyst (e.g., Shvo's catalyst) and used for reduction of glycolaldehyde in the present processes. Figure 5 shows the reaction scheme and observed yields of ethylene glycol for a transfer hydrogenation process step of the present invention. As shown in Figure 5, yields of ethylene glycol from the transfer hydrogenation reaction of glycolaldehyde as large as 50% are achievable. Table 1 summarizes the observed yields of ethylene glycol for a number transition metal transfer hydrogen catalysts. | |
With potassium carbonate In 1,4-dioxane at 70℃; for 2 - 5h; | 1.1.b 1.b. Effect of Base; [079] The use of a base to generate metal hydrides in situ from metal chlorides and methanol was explored. Figure 6 provides the reaction scheme for transfer hydrogenation in the presence of a base to generate ethylene glycol. In a standard procedure, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) followed by base (et3N, NaOH, KOH, Cs2CO3, Na2CO3 or K2CO3, 0.1 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. High yields were observed for certain bases, especially at lower temperatures, as shown in Table 2. At room temperature for some reaction conditions the amount of side products diminishes substantially, but ethylene glycol production is decreases after 3 hours and observed yields are lower. | |
With caesium carbonate In 1,4-dioxane at 70℃; for 2 - 5h; | 1.1.b 1.b. Effect of Base; [079] The use of a base to generate metal hydrides in situ from metal chlorides and methanol was explored. Figure 6 provides the reaction scheme for transfer hydrogenation in the presence of a base to generate ethylene glycol. In a standard procedure, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) followed by base (et3N, NaOH, KOH, Cs2CO3, Na2CO3 or K2CO3, 0.1 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. High yields were observed for certain bases, especially at lower temperatures, as shown in Table 2. At room temperature for some reaction conditions the amount of side products diminishes substantially, but ethylene glycol production is decreases after 3 hours and observed yields are lower. |
With potassium hydroxide In 1,4-dioxane at 70℃; for 2 - 5h; | 1.1.b 1.b. Effect of Base; [079] The use of a base to generate metal hydrides in situ from metal chlorides and methanol was explored. Figure 6 provides the reaction scheme for transfer hydrogenation in the presence of a base to generate ethylene glycol. In a standard procedure, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) followed by base (et3N, NaOH, KOH, Cs2CO3, Na2CO3 or K2CO3, 0.1 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. High yields were observed for certain bases, especially at lower temperatures, as shown in Table 2. At room temperature for some reaction conditions the amount of side products diminishes substantially, but ethylene glycol production is decreases after 3 hours and observed yields are lower. | |
With sodium hydroxide In 1,4-dioxane at 70℃; for 2 - 5h; | 1.1.b 1.b. Effect of Base; [079] The use of a base to generate metal hydrides in situ from metal chlorides and methanol was explored. Figure 6 provides the reaction scheme for transfer hydrogenation in the presence of a base to generate ethylene glycol. In a standard procedure, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) followed by base (et3N, NaOH, KOH, Cs2CO3, Na2CO3 or K2CO3, 0.1 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. High yields were observed for certain bases, especially at lower temperatures, as shown in Table 2. At room temperature for some reaction conditions the amount of side products diminishes substantially, but ethylene glycol production is decreases after 3 hours and observed yields are lower. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | In 1,4-dioxane at 70℃; for 2 - 5h; | 1.1.a 1.a. Transfer Hydrogenation Experiments; [075] In a typical experiment, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed out and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. Glycolaldehyde acetal and methylglycolate were obtained as the major by-products along with ethylene glycol. Yields of ethylene glycol ranging from 0-40% using RuCI2(PPh3)3, RuH2(PPh3)3, RuH2(PPh3)4, RuH(OAc)(PPh3)3, Ru(OAc)2(PPh3)3, Cp*lr(dpen)CI, Cp*Ru(OMe)2 and [Cp*lrCI2]2 were typically obtained. Substantial amounts of acetal were obtained primarily when RuCI2(PPh3)3, and particularly [Cp*lrCI2]2, were used. A typical chromatogram is shown in Figure 3 showing the production of ethylene glycol.[076] The transfer hydrogenation step was studied first in a separate set of experiments. Ethylene glycol was produced in varied yields. Under some experimental conditions, significant amounts of glycolaldehyde dimethylacetal and methyl glycolate were also formed as by-products. While acetal formation can be completely suppressed depending on the transition-metal complex used, formation of methyl glycolate is unavoidable and appears intrinsic to the overall process. Figure 4 provides a scheme showing the formation of methyl glycolate. The hydrogen produced in this transformation may be transferred by the metal catalyst (e.g., Shvo's catalyst) and used for reduction of glycolaldehyde in the present processes. Figure 5 shows the reaction scheme and observed yields of ethylene glycol for a transfer hydrogenation process step of the present invention. As shown in Figure 5, yields of ethylene glycol from the transfer hydrogenation reaction of glycolaldehyde as large as 50% are achievable. Table 1 summarizes the observed yields of ethylene glycol for a number transition metal transfer hydrogen catalysts. |
35% | With triethylamine In 1,4-dioxane at 70℃; for 2 - 5h; | 1.1.b 1.b. Effect of Base; [079] The use of a base to generate metal hydrides in situ from metal chlorides and methanol was explored. Figure 6 provides the reaction scheme for transfer hydrogenation in the presence of a base to generate ethylene glycol. In a standard procedure, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) followed by base (et3N, NaOH, KOH, Cs2CO3, Na2CO3 or K2CO3, 0.1 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. High yields were observed for certain bases, especially at lower temperatures, as shown in Table 2. At room temperature for some reaction conditions the amount of side products diminishes substantially, but ethylene glycol production is decreases after 3 hours and observed yields are lower. |
27% | With potassium carbonate In 1,4-dioxane at 20℃; for 2 - 5h; | 1.1.b 1.b. Effect of Base; [079] The use of a base to generate metal hydrides in situ from metal chlorides and methanol was explored. Figure 6 provides the reaction scheme for transfer hydrogenation in the presence of a base to generate ethylene glycol. In a standard procedure, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) followed by base (et3N, NaOH, KOH, Cs2CO3, Na2CO3 or K2CO3, 0.1 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. High yields were observed for certain bases, especially at lower temperatures, as shown in Table 2. At room temperature for some reaction conditions the amount of side products diminishes substantially, but ethylene glycol production is decreases after 3 hours and observed yields are lower. |
27% | With caesium carbonate In 1,4-dioxane at 20℃; for 2 - 5h; | 1.1.b 1.b. Effect of Base; [079] The use of a base to generate metal hydrides in situ from metal chlorides and methanol was explored. Figure 6 provides the reaction scheme for transfer hydrogenation in the presence of a base to generate ethylene glycol. In a standard procedure, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) followed by base (et3N, NaOH, KOH, Cs2CO3, Na2CO3 or K2CO3, 0.1 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. High yields were observed for certain bases, especially at lower temperatures, as shown in Table 2. At room temperature for some reaction conditions the amount of side products diminishes substantially, but ethylene glycol production is decreases after 3 hours and observed yields are lower. |
20% | With potassium hydroxide In 1,4-dioxane at 70℃; for 2 - 5h; | 1.1.a 1.a. Transfer Hydrogenation Experiments; [075] In a typical experiment, 120 mg (2.0 mmol based on monomer) of glycolaldehyde were weighed into a glass bomb fitted with a Teflon valve. The bomb was evacuated and refilled with argon and metal catalyst (0.02 mmol) was added under a counterflow of argon. The bomb was then fitted with a rubber septa and 5 ml_ of dry methanol were injected followed by 30 μl_ of dioxane (internal standard). The septa was replaced by a Teflon valve and the system was heated in an oil bath at 700C for 2-5 hrs. The system was cooled and a sample of this mixture was then syringed out and passed through a Stratopheres plug to remove the transition metal. The sample was analyzed by GC and ethylene glycol quantified. Glycolaldehyde acetal and methylglycolate were obtained as the major by-products along with ethylene glycol. Yields of ethylene glycol ranging from 0-40% using RuCI2(PPh3)3, RuH2(PPh3)3, RuH2(PPh3)4, RuH(OAc)(PPh3)3, Ru(OAc)2(PPh3)3, Cp*lr(dpen)CI, Cp*Ru(OMe)2 and [Cp*lrCI2]2 were typically obtained. Substantial amounts of acetal were obtained primarily when RuCI2(PPh3)3, and particularly [Cp*lrCI2]2, were used. A typical chromatogram is shown in Figure 3 showing the production of ethylene glycol.[076] The transfer hydrogenation step was studied first in a separate set of experiments. Ethylene glycol was produced in varied yields. Under some experimental conditions, significant amounts of glycolaldehyde dimethylacetal and methyl glycolate were also formed as by-products. While acetal formation can be completely suppressed depending on the transition-metal complex used, formation of methyl glycolate is unavoidable and appears intrinsic to the overall process. Figure 4 provides a scheme showing the formation of methyl glycolate. The hydrogen produced in this transformation may be transferred by the metal catalyst (e.g., Shvo's catalyst) and used for reduction of glycolaldehyde in the present processes. Figure 5 shows the reaction scheme and observed yields of ethylene glycol for a transfer hydrogenation process step of the present invention. As shown in Figure 5, yields of ethylene glycol from the transfer hydrogenation reaction of glycolaldehyde as large as 50% are achievable. Table 1 summarizes the observed yields of ethylene glycol for a number transition metal transfer hydrogen catalysts. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15% | With hydrogen; sodium methylate In methanol for 96h; | 2301.A Example 2301 ; Part A:; A mixture of 4-Chromanone 901A (0.912 g, 6.16 mmol), Pd/C (0.106 g),Glycoaldehyde (0.740 g, 6.16 mmols) 0.5 M NaOMe (2.6 mL) in MeOH (20 mL) was hydrogenated at 1 atm over 4 days. The reaction was passed through celite, washed with MeOH and concentrated. Purification by flash column chromatography (SiO2, 50% ethyl acetate in hexanes) to afford compound 1 (0.167 g, 15% yield) as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; In water; at 20℃; for 1h; | In a four necked round-bottomed glass reactor, equipped with magnetic stirrer, thermometer, condenser maintained at -75°C (dry ice-lsopropyl alcohol) and two addition funnels, 60 g of glycol aldehyde (1.0 mol) and 62 g of ethylene glycol (1.0 mol) were loaded, followed by 10 g of 37percent HCI water solution (0.10 mol HCI) at room temperature; after 1 hour under stirring, the formation of cyclic acetal (G) was complete; the reactor was thus cooled to 0°C with an ice water bath, then a solution of 44 g (1.1 mol) of NaOH (s) and 44 ml of distilled water H2O was added in half an hour. After a slight exothermicity, at 0°C, 216 g (1.0 mmol) of (A) were slowly added. At the end of the addition, the reaction mixture was allowed to reach 20°C, and stirred for another 2 hours. The crude mixture was extracted three times with tetrahydrofuran (THF). The combined THF extracts were dehydrated with MgSO4, filtered and fractionally distilled, collecting 247 g of the partially hydrogenated ether (H) (yield 77percent mol). The aldehyde group of adduct (H) was deprotected (quantitatively) obtaining the corresponding aldehyde (J) by hydrolysis in acidic conditions (diluted HCI). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; at 300℃; for 0.3h;Stainless steel flow reactor; | Example 4; Continuous reactions using the Materials of Example 2 were completed. The yields of products obtained from a continuous run are presented in Table 3. A reaction mixture under high pressure (from approximately 1500 psi to 3500 psi) was pumped sequentially through a high temperature zone (from approximately 200 C. to 325 C.), a heat exchanger, a backpressure regulator, and then into a collection vessel. The reaction mixture was generated by pumping an aqueous solution of glucose at room temperature into a heated source of 2-propanol (temperature from approximately 275 C. to 325 C.) which was being pumped into the high temperature zone. aContinuous reaction pumped through a stainless steel tube having about a 5 min residence time and a length to diameter ratio of about 20. Temperature was 300 C., and the sample was collected over a period of 18 min. Glucose input during this time was 0.64 g and solvent included 32 mL of 2-propanol/5% water. ball yields given in grams per gram starting material cDetected by NMR in the D2O solution as the hydrate but reported as the aldehyde. disopropyl ester tentatively assigned as isopropyl glycolate eisopropyl ester tentatively assigned as isopropyl acetate funidentified products not soluble in alcohol gunidentified products soluble in alcohol htotal identified products derived from carbohydrate material iproduced by the oxidation of 2-propanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 25 %Chromat. 2: 19 %Chromat. 3: 10 %Chromat. 4: 7 %Chromat. | With zeotype catalyst Sn-Beta (Si/Sn = 400) In methanol at 120℃; for 16h; Autoclave; Inert atmosphere; | |
1: 30 %Chromat. 2: 14 %Chromat. 3: 12 %Chromat. 4: 8 %Chromat. | With zeotype catalyst Sn-Beta (Si/Sn = 400) In methanol at 140℃; for 16h; Autoclave; Inert atmosphere; | |
1: 27 %Chromat. 2: 16 %Chromat. 3: 7 %Chromat. 4: 6 %Chromat. | With zeotype catalyst Sn-Beta (Si/Sn = 400) In methanol at 160℃; for 16h; Autoclave; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 26 %Chromat. 2: 13 %Chromat. 3: 8 %Chromat. | With zeotype catalyst Sn-Beta (Si/Sn = 400) In methanol at 100℃; for 16h; Autoclave; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: N-benzyl-2-nitroaniline With hydrogenchloride; indium In water at 100℃; for 0.5h; Stage #2: Glycolaldehyde In water at 100℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Glycolaldehyde (645 mg, 10.7 mmol) was added to a solution containing aniline (1, 1.00 g, 10.7 mmol) in DCE (30 mL) . The solution was stirred at room temperature in argon atmosphere for 30 min. Sodium triacetoxyborohydride (2.61 g, 12.3 mmol) was then added portion-wise. The reaction mixture was further stirred for 4 h before and quenched with NaHC03 to pH = 9.0. The reaction mixture was extracted with mixed solvent (CHC13 : i-PrOH = 4:1, 30 mL x 3) . The organic layer was dried (anhydrous sodium sulfate) and concentrated in vacuo. The crude product was chromatographed on silica gel (CH2Cl2/MeOH, 20:1). to yield target compound 2. Yield 1.061 g, 72%. Rf = 0.45, 1H NMR (CHC13, 400 MHz): delta 7.24 (dd, J = 8.8, 7.4 Hz, 2H) , 6.80 (t, J = 7.4 Hz, 1H) , 6.69 (d, J = 8.8, 2H) , 3.81 (t, J = 5.2 Hz, 2H) , 3.30 (t, J = 5.2 Hz, 2H) , 2.6 (br s, 1H); 13C NMR (CHC13, 100 MHz): delta 148.2, 129.4, 118.0, 113.3, 61.2, 46.1; [M+H]+ = 138.08 (APCI+) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 14.84℃; for 4h; Irradiation; | 2.2. Typical conditions for glucose conversion reaction General procedure: Photocatalytic reactions were carried out at 288 K in a Pyrex reaction cell connected to a closed gas circulation and vacuum system. A 300 W top-irradiated xenon lamp was used as a light source. Prior to illumination, the system was deaerated by evacuation. Typically, 0.1 g of catalyst was suspended in a 100 mL glucose solution (0.0125 mol L-1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide; copper In acetonitrile at 80℃; for 24h; Sonication; Sealed tube; | 2.2. Glycerol oxidation General procedure: Nano-Au catalyst (20 mg, 0.2-20.0 lmol Au) was suspended ina mixture of 1.0 mL of 30% hydrogen peroxide (10 mmol H2O2) and 0.5 mL (0.5-13.6 mol/L) glycerol (Fisher BioReagents - GlycerolFor Molecular Biology) by sonication at room temperature for10 min (RK 52 H, Bandolin Electronics, 35 kHz). Reagents were stirredat 770 rpm in a sealed tube (septa system) placed in a thermostatedoil bath at 80 C for 24 h. The resulted reaction mixture wascentrifuged and decantated. The supernatant was dissolved intodeuterated water and analyzed using 1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide at 60℃; for 24h; Sonication; Sealed tube; | 2.2. Glycerol oxidation General procedure: Nano-Au catalyst (20 mg, 0.2-20.0 lmol Au) was suspended ina mixture of 1.0 mL of 30% hydrogen peroxide (10 mmol H2O2) and 0.5 mL (0.5-13.6 mol/L) glycerol (Fisher BioReagents - GlycerolFor Molecular Biology) by sonication at room temperature for10 min (RK 52 H, Bandolin Electronics, 35 kHz). Reagents were stirredat 770 rpm in a sealed tube (septa system) placed in a thermostatedoil bath at 80 C for 24 h. The resulted reaction mixture wascentrifuged and decantated. The supernatant was dissolved intodeuterated water and analyzed using 1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With mesoporous Zr-SBA-15 at 240℃; for 1h; Inert atmosphere; | 2.4. Catalytic reactions General procedure: Reactions were carried out in a 100 mL stirred Parr micro reactor,whereby the catalyst was suspended in a solution of biomasssubstrate in methanol (20 mL) and the reactor was charged with400 psi N2 initially and then heated at a ramp rate of 10 °C/minuntil the desired set temperature was reached. During the reaction,mixing was achieved through an internal propeller operating at 700 RPM. Once the set temperature was attained, the reactorwas held for the set reaction time, and then quenched quickly inan ice bath to stop the reaction. The reactor was cooled toapproximately 25 °C before being vented after the gas pressurewas recorded. The reactor was then immediately broken downand the solid residue remaining in the reactor was recovered anddried. The aqueous and solid fractions were separated using acentrifuge |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In aq. phosphate buffer; at 85℃; for 24h;pH 7.4; | Pyrazine derivatives were synthesized from a one-pot reaction, in which 1,3-dihydroxyacetone, glycolaldehyde, and 2-aminoacetamidine-dihydrobromide (0.10 M 1:1:1 ratio) were mixed in aqueous solution with sodium phosphate (0.25 M) atpH 7.4 by addition of NaOH, then heated to 85 C for 24 h. In a2-mL microvial, reaction contents were de-aerated and purged with nitrogen before being sealed under vacuum. A 1.0 mL aliquot of the product mixture was diluted with 8 mL of water,and a 5 mL portion was then desalted on a 20 mL Discovery DSC-18 column (Supelco, Bellefonte, PA, USA). Material was eluted with 36 mL water and 44 mL 50% methanol/water, collected in 20 separate fractions. Salt-free fractions 10-20(from 37-80 mL eluent) were combined and concentrated to 0.5 mL syrup using a CentriVap centrifuge. After storage at -20 C, the mixture was suspended in 200 muL water, and 50 muL aliquots were further diluted in 300 muL water for adequate ampoule sampling volume. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 500℃; Pyrolysis; | 2.2. micro-pyrolyzer-GC/FID experiments General procedure: The pyrolysis and catalytic pyrolysis experiments were conducted using a single-shot micro-pyrolyzer equipped with an auto sampler (Frontier Laboratories, Japan). The micro-pyrolyzer was directly connected to a GC analyzer with a FID, which was automatically conducted by the operation control in a combination system between the micro-reactor and gas analyzer. For the experimental conditions, the furnace was mainatined at a temperature of 500° C. The reactant of about 500 g was first placed into a stainless steel sample cup and then the catalyst of about 5 g was loaded at upper of reactant. Finally, the quartz wool was put at top of the sample cup and thus both the catalyst and reactant were fixed within sample cup, which was dropped into the furnace of pyrolyzer with very short drop time (with unitof milliseconds) under the flow of 20 cm/s helium gas. In product analysis, the products were separated using an alloy capillary column (Ultra Alloy-1701, Frontier Laboratories, Japan) with a carrier gas flow of 1 ml/min. For GC conditions, the injector temperature and split ratio were 300 °C and 1:100, respectively, and the oven temperature program began at 35 °C, held 3 min at 35 °C and then heated to 300 °C at 5 C/min, held for 4 min at that temperature. |
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 |
---|---|---|
In water at 14.84℃; for 12h; Sonication; Inert atmosphere; Irradiation; Electrolysis; | 2.2.1. Photoreforming experiments General procedure: Kinetic experiments were performed in a Pyrex top-irradiationphoto-reactor connected to a closed gas-circulation system [18].The setup is equipped with facilities for online gas-analysis andliquid-phase sampling. Irradiation is provided by a 300W Xe lampwith a cold mirror 1 (CM 1). A water filter with quartz windowscloses the top of the photo-reactor. The photon flux within the reactor at water level is 8.08 x 1017 s-1 (λ < 390 nm). Typically,75 mg of photocatalyst were ultrasonically dispersed in 100 mLof a 20 mM aqueous reactant solution. The system was deaeratedby four consecutive evacuations and Ar filling cycles. All reactionswere carried out at 288 K and an Ar pressure of 1 bar. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 24 μmol 2: 45 μmol 3: 5 μmol 4: 25 μmol 5: 275 μmol 6: 30 μmol | In water at 14.84℃; for 12h; Sonication; Inert atmosphere; Irradiation; Electrolysis; | 2.2.1. Photoreforming experiments General procedure: Kinetic experiments were performed in a Pyrex top-irradiationphoto-reactor connected to a closed gas-circulation system [18].The setup is equipped with facilities for online gas-analysis andliquid-phase sampling. Irradiation is provided by a 300W Xe lampwith a cold mirror 1 (CM 1). A water filter with quartz windowscloses the top of the photo-reactor. The photon flux within the reactor at water level is 8.08 x 1017 s-1 (λ < 390 nm). Typically,75 mg of photocatalyst were ultrasonically dispersed in 100 mLof a 20 mM aqueous reactant solution. The system was deaeratedby four consecutive evacuations and Ar filling cycles. All reactionswere carried out at 288 K and an Ar pressure of 1 bar. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 614 μmol 2: 421 μmol 3: 158 μmol | In water at 14.84℃; for 12h; Sonication; Inert atmosphere; Irradiation; Electrolysis; | 2.2.1. Photoreforming experiments General procedure: Kinetic experiments were performed in a Pyrex top-irradiationphoto-reactor connected to a closed gas-circulation system [18].The setup is equipped with facilities for online gas-analysis andliquid-phase sampling. Irradiation is provided by a 300W Xe lampwith a cold mirror 1 (CM 1). A water filter with quartz windowscloses the top of the photo-reactor. The photon flux within the reactor at water level is 8.08 x 1017 s-1 (λ < 390 nm). Typically,75 mg of photocatalyst were ultrasonically dispersed in 100 mLof a 20 mM aqueous reactant solution. The system was deaeratedby four consecutive evacuations and Ar filling cycles. All reactionswere carried out at 288 K and an Ar pressure of 1 bar. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
8% | With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 336h; Sealed tube; | B19 Preparation of compound 301 In a sealed tube, 3-fluoro-1-methylaniline (60.4 jiL, 0.536 mmol) was added to asolution of intermediate 191 (177 mg, 0.536 mmol) and glycolaldehyde dimer (32.2mg, 0.268 mmol) in hexafluoroisopropanol (1.07 mL). The mixture was stirred at roomtemperature for 14 days. The resulting solution was concentrated under reduced pressure. The crude product was purified by reverse phase (Stationary phase: X-BridgeC18 Sjim 30*150mm, Mobile phase: Gradient from 85% aq. NH4HCO3 0.2% , 15% ACN to 45% aq. NH4HCO3 0.2% , 55% ACN) to give compound 301 (18.6 mg, 8%,MP :315°C, DSC) as a yellow powder |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: formaldehyd; Glycolaldehyde With hydroxyapatite In water at 80℃; for 42h; Stage #2: acetic anhydride With pyridine In water at 80℃; for 0.25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; | ||
In tetrahydrofuran at 0 - 20℃; for 12h; Inert atmosphere; | ||
In tetrahydrofuran at 0 - 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32.7% | With Sn-BEA zeolite (Si/Sn=125) at 160℃; for 20h; Sealed tube; | 3A-3G Example 3A For the preparation of valine hydroxy analogue, 10 g of an acetone/GA solution composed of 0.1 g GA, 5 g acetone and 4.9 g anhydrous methanol was pre-mixed and added to a stainless steel pressure vessel (40 cc, Swagelock) along with 0.50 g of post-synthesized Sn-BEA (Si/Sn = 125). This batch reactor was then sealed and placed in a pre-heated oil bath at 160 °C under 700 rpm stirring and left to react for 20 h. Upon experiment completion, the vessel was rapidly cooled in cold water. The reactor was then opened, the reaction mixture recovered by filtration and the compounds present were identified and quantified on a GC-MS (Agilent 6890 with a Zebron ZB-5MS column (Phenomenex) equipped with an Agilent 5973 mass selective detector) and a GC-FID (Agilent 7890 with a Zebron ZB-5 column (Phenomenex) equipped with a flame ionization detector). Pure standard of hydroxy-analogue of valine (Enamine, 95%), glycolaldehyde dimethyl acetal (Sigma Aldrich, 98%) and glycolaldehyde (>99%) was used to quantify the alpha-hydroxy reaction product yield and the amount of unconverted substrate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49.9% | With Sn-BEA zeolite (Si/Sn=125); at 160℃; for 20h;Sealed tube; | For the preparation of phenylalanine hydroxy analogue, 10 g of a benzaldehyde/GA solution composed of 0.1 g GA, 5 g benzaldehyde and anhydrous methanol was pre-mixed and added to a stainless steel pressure vessel (40 cc, Swagelock) along with 0.50 g of post-synthesized Sn-BEA (Si/Sn = 125). This batch reactor was then sealed and placed in a pre-heated oil bath at 160 C under 700 rpm stirring and left to react for 20 h. Upon experiment completion, the vessels were rapidly cooled in cold water. The reactor was then opened, the reaction mixture recovered by filtration and the products identified and quantified on a GC-MS (Agilent 6890 with a Zebron ZB-5MS column (Phenomenex) equipped with an Agilent 5973 mass selective detector) and a GC-FID (Agilent 7890 with a Zebron ZB-5 column (Phenomenex) equipped with a flame ionization detector). Pure standard of hydroxy-analogue of phenylalanine (ArkPharm, 97%), glycolaldehyde dimethyl acetal (Sigma Aldrich, 98%) and glycolaldehyde (>99%) was used to quantify the product yield and unconverted substrate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With diethylenetriaminopentaacetic acid; sodium cyanoborohydride at 37℃; for 2h; Darkness; | Determination of glycolaldehyde General procedure: To prepare the internal standard, 20 mM 4-aminobenzoic-2,3,5,6-d4 acid was treated with 10 mM GA and 25 mM NaCNBH3 at 37 °C for 2 h in the dark. Isotope-labeled GA-ABA was purified by HPLC, evaporated, and dissolved in water. The concentration of the products was measured by absorbance at 280 nm using ABA as a standard. For GA determination, 15 μl of samples was incubated with 25mM ABA and 25mM NaCNBH3 in 100 μl of 0.5 mM diethylenetriamine-N,N,N’,N’,N’-pentaacetic acid at 37 °C for 2 h in the dark. The internal standard, [2H4]GA-ABA, was added to the samples prior to incubation. After the reaction, methanol (300 μl), chloroform (100 μl), and water (300 μl) were added and vortexed. After centrifugation, the upper phase was collected, evaporated, and then reconstituted in 100 μl of H2O:MeOH (1:1). The ABA derivative of GA was measured using a stable isotope dilution-based LC-ESI-MS/MS technique. The column and gradient conditions were the same as those for measurement of the DNPH derivatives. A mass spectrometry analysis in positive ion mode was performed in multiple reaction monitoring (MRM) mode (cone potential, 30 eV; collision energy, 15 eV). MRM transitions monitored were as follows: [2H4]GAABA, m/z 186.4 > 124.3; GA-ABA, m/z 182.4 > 120.3. The amount of the GA-ABA was quantified by the ratio of the peak area of GA-ABA and of the GA-ABA stable isotope. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.3% | With manganese; chromium; hydrogen; nickel; aluminium In water at 150℃; Autoclave; | 1-23 Example 1 General procedure: Add 100g (1.1628mol) to the autoclave with water added as a solvent in advanceAnhydrous piperazine and 73.3g (1.2217mol) glycolaldehyde, add 10g containing nickel, aluminum, manganese,The Raney nickel catalyst of chromium, the lid of the reaction kettle is tightened, and the pressure of hydrogen is charged to 3.0MPa after nitrogen replacement, stirring is started, and the stirring rate is controlled at 1000rpm,The reaction is raised to 150,During the reaction, pay attention to continuously replenish hydrogen to maintain the pressure at 3.0MPaUntil the pressure no longer drops.Then the reaction was cooled to room temperature and filtered,The filtrate is distilled under reduced pressure at 21002200Pa,Collecting fractions with a temperature range of 136-140°C, a total of 139.0g fractions were obtained,The molar yield (relative to piperazine) was 92.0%, and the gas phase purity was 99.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-Cyclobutyl-2-oxoacetic acid With sodium hydroxide In water Stage #2: Glycolaldehyde With 3-methyl-2-oxobutanoate hydroxymethyltransferase from E. coli wild type; cobalt(II) chloride In water for 24h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tin-molybdenum mixed oxide In water at 150℃; for 3h; | 2.2. Conversion of xylose All experiments were performed in vials of 4 mL under magnetic stirring and heating applying several different reaction times. Solutionsof 0.016 g of xylose in 2 mL of deionized water and, for some experiments,catalysts (1.5 ×10-3 g), were used for reactions at 110, 130 and150 °C, applying reaction times of 0.5-3 h. The conversion, yield and selectivity were calculated from the results of the quantification by HPLC [13]. For that, the solution after the reaction was passed through a 0.45 μm Millipore filter before injection into a CTO-20A HPLC systemfitted with an RID-10A (Shimadzu) equipped with a MetaCarb 87 H column (300 mm × 7.8 mm). Analyses were conducted at 50 °C with aflow rate of 0.70 mL.min 1 using acidified water (H2SO4 5.10 -3 mol.L -1). The products detected were quantified using calibration curves obtained from standards. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tin-molybdenum mixed oxide In water at 150℃; for 2h; | 2.2. Conversion of xylose All experiments were performed in vials of 4 mL under magnetic stirring and heating applying several different reaction times. Solutionsof 0.016 g of xylose in 2 mL of deionized water and, for some experiments,catalysts (1.5 ×10-3 g), were used for reactions at 110, 130 and150 °C, applying reaction times of 0.5-3 h. The conversion, yield and selectivity were calculated from the results of the quantification by HPLC [13]. For that, the solution after the reaction was passed through a 0.45 μm Millipore filter before injection into a CTO-20A HPLC systemfitted with an RID-10A (Shimadzu) equipped with a MetaCarb 87 H column (300 mm × 7.8 mm). Analyses were conducted at 50 °C with aflow rate of 0.70 mL.min 1 using acidified water (H2SO4 5.10 -3 mol.L -1). The products detected were quantified using calibration curves obtained from standards. |
Tags: 141-46-8 synthesis path| 141-46-8 SDS| 141-46-8 COA| 141-46-8 purity| 141-46-8 application| 141-46-8 NMR| 141-46-8 COA| 141-46-8 structure
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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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