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CAS No. : | 108-32-7 | MDL No. : | MFCD00005385 |
Formula : | C4H6O3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RUOJZAUFBMNUDX-UHFFFAOYSA-N |
M.W : | 102.09 | Pubchem ID : | 7924 |
Synonyms : |
|
Num. heavy atoms : | 7 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.75 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 3.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 21.99 |
TPSA : | 35.53 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -7.21 cm/s |
Log Po/w (iLOGP) : | 1.27 |
Log Po/w (XLOGP3) : | -0.41 |
Log Po/w (WLOGP) : | 0.54 |
Log Po/w (MLOGP) : | -0.38 |
Log Po/w (SILICOS-IT) : | 0.84 |
Consensus Log Po/w : | 0.37 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.21 |
Solubility : | 62.3 mg/ml ; 0.61 mol/l |
Class : | Very soluble |
Log S (Ali) : | 0.13 |
Solubility : | 137.0 mg/ml ; 1.34 mol/l |
Class : | Highly soluble |
Log S (SILICOS-IT) : | -0.16 |
Solubility : | 70.5 mg/ml ; 0.69 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.2 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313 | UN#: | N/A |
Hazard Statements: | H315-H319 | 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 |
---|---|---|
54.8% | at 130℃; for 8 h; Autoclave; High pressure | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13.2% | at 130℃; for 8 h; Autoclave; High pressure | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min. |
12.5% | at 130℃; for 8 h; Autoclave; High pressure | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min. |
5.8% | at 130℃; for 8 h; Autoclave; High pressure | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min. |
23% | at 130℃; for 8 h; Autoclave; High pressure | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min. |
7.8% | at 130℃; for 8 h; Autoclave; High pressure | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52.4% | at 130℃; for 8 h; Autoclave; High pressure | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99percent) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10°C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25μm) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60°C for 3min and then was programmed to rise to 80°C at the rate of 5°Cmin−1, and further reached 220°C at the rate of 30°Cmin−1 and remained at that temperature for 3min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62.5 - 74 %Chromat. | at 170℃; for 8 h; | This example describes the preparation of dihexyl carbonate from propylene carbonate and hexanol. Propylene carbonate (1.02 g; 10 mmol), hexanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 170° C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With triethylamine; adenine In neat (no solvent) at 120℃; for 18h; regioselective reaction; | General procedure for the synthesis of oxazolidinones General procedure: An 8 mL vial was charged with adenine (0.05 mmol, 6.7 mg), Et3N (0.5 mmol, 69 μL), aryl amine (1 mmol) and cyclic carbonate (6 mmol). The mixture was heated at 110 °C for 18 h, after which time 5 mL of water was added. The organic layer was extracted with dichloromethane (3 × 5 mL). The combined organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate = 5:1 as eluent). |
92% | With IL(OAc-)-MIL-101-NH2 In neat (no solvent) at 140℃; for 9h; | |
72.7% | With C19H31KNO5(1+)*2C2H3O2(1-)*H(1+) at 130℃; for 5h; |
With lithium chloride at 176℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With palladium 10% on activated carbon; oxygen; sodium acetate; potassium iodide; In 1,2-dimethoxyethane; at 100℃; under 10343.2 Torr; for 8h;Autoclave; Inert atmosphere; | General procedure: In a 100 mL stainless steel autoclave, diol (5mmol), catalyst (10 % Pd/C, 0.5 mol %), KI (0.09 mmol), base (1.25 mmol),solvent (10 mL) were added. The autoclave was closed, flushed with nitrogen,pressurized with O2 (33 psi) and CO (167 psi) and reaction mixturewas stirred with a mechanical starrer (520 rpm) at desired temperature forappropriate time period. After completion of reaction, the reactor was thencooled to room temperature, degassed carefully and opened. The reaction mixturewas filtered and the solvent was evaporated under vacuum. The reaction mixturewas analyzed by GC analysis (Perkin-Elmer, Clarus 400) equipped with a flameionization detector (FID) and a capillary column (Elite-1, 30 m × 0.32 mm ×0.25 mum). Purification of residue was carried out by column chromatography(silica gel 100-200 mesh, petroleum ether/ethyl acetate) to afford thecorresponding products in good to excellent yield. The prepared compounds werecharacterized by 1H NMR (Varian 200 MHz NMR Spectrometer), 13CNMR spectra (50 MHz) and GC-MS (Shimadzu GC-MS QP 2010) (Rtx-17, 30 m × 25mmID,film thickness 0.25 mum df) (column flow- 2 mL/min, 80 C to 240 C at 10/min.rise.) which were consistent with those reported in the literature |
With oxygen; sodium carbonate; copper dichloride; In acetonitrile; at 100℃; under 22502.3 Torr; for 3h;Autoclave; | General procedure: 2.2.1 Synthesis of 4-methyl-1,3-dioxolan-2-one :In a typical experiment the glass vial was charged with solvent (CH3CN, 9.0 mL), catalyst (CuCl2, 0.60 mmol), co-catalyst (Na2CO3, 0.60 mmol) and 1,2-PD (10 mmol). The vial was introduced into the autoclave which was sealed and charged with O2 (0.5 MPa) and CO up to a total pressure of 3 MPa.Under these conditions, also taking into account the free volume ofthe autoclave and the stoichiometry of the carbonylation process (Eq.(4)), the diol is thelimiting reagent. The autoclave was heated at 100?C and allowed to react for 3 h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With 4-dimethylaminopyridine at 60℃; for 40h; | |
100% | With triphenylphosphine; sodium iodide; phenol at 120℃; for 4h; | |
100% | at 120℃; for 4h; |
100% | at 110℃; for 3h; | |
100% | With 4-dimethylaminopyridine; binaphthyldiamino Schiff base In 1,2-dichloro-ethane at 120℃; for 48h; | |
100% | With 4-dimethylaminopyridine; 4-methoxy-phenol In dichloromethane at 120℃; for 48h; | |
100% | With triethylamine In dichloromethane at 100℃; for 16h; | |
100% | With 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate In dichloromethane at 120℃; for 8h; | |
100% | With 4-dimethylaminopyridine; C19H26CoN4O2(3+) at 120℃; for 3h; | |
100% | With L-histidine at 130℃; for 48h; Autoclave; chemoselective reaction; | |
100% | With trimethyl-(2-hydroxyethyl)ammonium chloride; anhydrous zinc bromide at 110℃; for 1h; Autoclave; neat (no solvent); | |
100% | With N,N,N-tributyl-1-butanaminium iodide; 1,3,5-trimethyl-benzene; 2-hydroxyresorcinol In butanone at 45℃; for 18h; Autoclave; | |
100% | With 4C21H14N2O5(4-)*8Zn(2+)*8H2O; N,N,N-tributyl-1-butanaminium iodide In neat (no solvent) at 45℃; for 66h; | |
100% | With C18H14Cl2N4O4Zn; N,N,N-tributyl-1-butanaminium iodide at 80℃; for 20h; Green chemistry; | |
100% | With porous poly(ionic liquid) prepared by the anion exchange of poly(bisvinylimidazolium-base disalicylate) and NaCl at 140℃; for 6h; | |
100% | With [Zn(Me)(κ3-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1-[4-(dimethylamino)phenyl]ethanolato-μ-O})Zn(Me)2]; tetrabutylammonium bromide at 50℃; for 15h; | |
100% | With tetrabutylammonium bromide at 80℃; | General procedure for the carboxylation of oxiranes 4a-4g. General procedure: An RLP15ML 15-mL glass low-pressure reactor equipped with a gas inlet system, pressure gage, and magnetic stirrer was charged with 0.2 mmol of oxirane 4a-4g, 0.004 mmol of catalyst 1 or 3 or 3.0 mg of CuCa-LSF (2), and 0.003 mmol of TBAB. The reactor was filled thrice with CO2, the gas pressure was adjusted to 2 atm, and the mixture was stirred for 15 h at 80°C. The mixture was then cooled to room temperature, the liquid part was separated by centrifugation and the product was isolated by silica gel column chromatography using petroleum ether as eluent and dried under reduced pressure. The spectral characteristics of compounds 5a-5g were in agreement with published data [29, 46]. |
100% | With tetrabutylammonium bromide In N,N-dimethyl-formamide at 80℃; | |
100% | at 130℃; for 24h; Ionic liquid; Autoclave; | Synthesis of carbonates 5, 7a-i, and 9 from epoxides (general procedure). General procedure: A corresponding ammonium salt (0.015 mmol) was placed into a 10-mL autoclave, followed by the addition of an epoxide (3 mmol). The autoclave was filled with CO2 (20 or 56 atm.) and heated in a thermostat at 120 or 130 °C (see Table 1) for 24 h. After the completion of the process, the autoclave was cooled to room temperature, excess CO2 pressure was vented, and the residue was analyzed by 1H NMR spectroscopy. The spectral characteristics of carbonates 5, 7a-i, and 9 correspond to those published earlier.18,21,25,28-31 |
100% | With tetrabutylammonium bromide In neat (no solvent) at 28℃; for 24h; | |
100% | With tetrabutylammonium bromide In neat (no solvent) at 50℃; Schlenk technique; | |
99% | at 120℃; for 0.666667h; other catalysts, var. of conditions; | |
99% | at 120℃; for 0.666667h; other catalysts, various conditions; | |
99% | With tetrabutylammonium bromide; triphenylphosphine; zinc at 120℃; for 1h; | |
99.1% | at 115℃; for 6h; | |
99.3% | With poly(4-vinylbenzyltriphenyl phosphorous chloride)-co-poly(ethylene dimethacrylate) at 159.84℃; for 3h; | |
99% | With meta-(trimethylammonio)phenolate betaine at 120℃; for 24h; Autoclave; | |
99% | With carboxyl-group-functionalized imidazolium-based ionic liquid grafted on silica gel at 110℃; for 3h; | |
99% | With MCM-41-pr-TMEDA(+)Cl(-) at 120℃; for 6h; Autoclave; | |
99% | With 5,10,15,20-tetrakis[3-(6-tributylammoniohexyloxy)phenyl]porphyrin magnesium(II) tetrabromide at 120℃; for 6h; Autoclave; Neat (no solvent); | |
99% | With cyanocobalamine; N,N,N-tributyl-1-butanaminium iodide at 0 - 140℃; for 6h; Autoclave; Green chemistry; | |
99% | With polyionic liquid copolymerized with 1-vinyl-3-carboxymethylimidazolium bromide using divinylbenzene at 130℃; for 4h; | |
99% | With bis(η5-cyclopentadienyl) titanium dichloride; potassium iodide In tetrahydrofuran at 150℃; for 4h; Autoclave; | |
99% | With 4-dimethylaminopyridine; C16H21BrCl2CoN5O2 at 130℃; for 5h; Heating; | |
99.7% | With N,N,N-tributyl-1-butanaminium iodide at 140℃; for 8h; | |
99% | With 1-butyl-3-methyl-1H-imidazol-3-ium bromide; anhydrous zinc bromide at 120℃; for 4h; Autoclave; | General procedure: For a typical reaction of CO2with epoxides, ZnBr2(11.3 mg,0.05 mmol), [BMIM]Br (65 mg, 0.3 mmol) and epoxides (PO: 20 ml,0.286 mol; or ECH: 23.61 g, 0.255 mmol) were charged into a100 ml stainless steel autoclave equipped with a magnetic stirrerin sequence. The 3.0 MPa of CO2was filled into the reaction ves-sel which was then heated to 120C for 4 h. Once the reaction iscompleted, the vessel was cooled to room temperature and thegas was released slowly. Then the liquid phase was analyzed byHP7890A/5975C GC-MS. The unreacted substrate was then dis-tilled out from the mixture, and the product was obtained. Theenantiomeric purity of the mixture was analyzed by HP7890A GCequipped with a chiral DEX120 chromatography column. |
99% | With 1,8-Octanediol; [Cr(bis(8-hydroxyquinolinyl)butylamine)OAcF(ethanol)]; tetra-n-butyl-ammonium chloride In neat (no solvent) at 100℃; for 4.5h; | |
99% | With 5,10,15,20-tetrakis[3-(6-tributylammoniohexyloxy)phenyl]porphyrin magnesium(II) tetrabromide at 120℃; for 6h; Autoclave; | 17 General procedure: Cyclic carbonates (3a, 3b, 3c, 3d, 3e) were synthesized as described in Example 1, except that a catalyst wasmagnesium-porphyrin complex 1d (0.005 mol % to an epoxide), a pressure after carbon dioxide charge was 1.5 MPaand the type of an epoxide and a reaction time were as shown in Table 2. Each compound obtained was purified bysilica gel column chromatography and an isolation yield was determined. The results are shown in Table 2.Example 21[0116]In a 30 mL autoclave were placed epoxide 2a (10.0 mmol) and zinc-porphyrin complex 1a as a catalyst [0.001mmol (0.01 mol % to 2a)], and the autoclave was filled with carbon dioxide to a pressure of 1 MPa. The mixture wasstirred at 120 °C for 3 hours. The autoclave was cooled in an ice bath for 30 min, and then excessive carbon dioxidewas purged. To the crude product, 2-methoxynaphthalene was added as an internal standard, and then an NMR yieldwas determined. An yield of cyclic carbonate 3a was 80 %. The reaction conditions and the yield are also shown in Table 1. |
99% | With tri-n-butyl(2-hydroxyethyl)phosphonium iodide In neat (no solvent) at 90℃; for 3h; | |
99% | With tri-n-butyl(2-hydroxyethyl)ammonium iodide In neat (no solvent) at 90℃; for 2h; Autoclave; | |
99% | With 1,8-Octanediol; [Cr(babhq)OC(O)CF3]; tetra-n-butyl-ammonium chloride at 100℃; for 16h; Autoclave; | 1-1-5 Example 1-1-5 Synthesis of Cyclic Propylene Carbonate with the Complex [Cr(Babhq)OC(O)CF3] from Example 1-1 in the Presence of TBACl and 1,8-Octanediol Cyclic propylene carbonate was prepared according to formula (LVIII) by reacting propylene oxide with CO2. The letters given in the formula (LVIII) refer here to the designation of the atoms for the signal assignment in the NMR spectra. [0231] Cr(III) catalyst [Cr(babhq)OC(O)CF3] (10.6 mg, 0.020 mmol), tetrabutylammonium chloride (TBACl, 24.0 mg, 0.086 mmol), 1,8-octanediol (126 mg, 0.862 mmol) and propylene oxide (9.4 mL, 133 mmol) were charged in a 160 mL autoclave, equipped with a hollow shaft stirrer, and contacted with CO2 (20 bar) at room temperature (molar ratio propylene oxide/catalyst/TBACl=4304/1/4.1). The reaction mixture was then heated to 100° C. (over a period of 10 min) and stirred at 700 rpm for 16 hours. The autoclave was then cooled to 15° C. with the aid of an ice bath and the remaining CO2 excess pressure was slowly released. After opening the autoclave, an NMR sample was taken for quantitative analysis and was measured in CDCl3. [0232] Amount of unreacted propylene oxide: <1% [0233] Yield of cyclic propylene carbonate: >99% [0234] The residue remaining was a solution which was yellow-orange due to the catalyst and which was transferred to a round-bottom flask. After distillative removal of the volatile components on a rotary evaporator in a water bath (50° C.), the cyclic propylene carbonate was obtained as a yellow-orange liquid. [0235] A sample was dissolved in CDCl3 and analyzed by 1H-NMR spectroscopy. [0236] Only the characteristic signals of the cyclic propylene carbonate were observed. [0237] 1H-NMR (400 MHz, CDCl3) δ (ppm)=4.83-4.90 (1H, m, HB), 4.57 (1H, dd, HA), 4.04 (dd, HA), 1.49 (3H, d, CH3). |
99% | With meso-tetraphenylporphyrinatooxidovanadium(IV); tetrabutylammonium bromide at 150℃; for 5h; Autoclave; | |
99% | With graphene oxide grafted 3-(2-hydroxylethyl)-1-propylimidazolium bromide at 140℃; for 4h; Autoclave; | 2.3. Typical procedure for the cycloaddition of CO2with epoxide The cycloaddition reaction of epoxide with CO2to form cycliccarbonate was performed in a 50 mL stainless steel autoclaveequipped with a magnetic stirrer and a thermocouple. In a typicalrun, the reactor was charged with propylene oxide (PO, 214 mmol)and catalyst (0.4 g, 0.35 mol%). After the reactor was purged threetimes with CO2and pressurized to 2.0 MPa, the resultant mixturewas heated to 140C and stirred for 4 h. At the end of the reac-tion, the reactor was cooled in an ice water bath and the residualCO2was slowly vented. After being separated from the catalyst bya centrifuge, the products were analyzed by a gas chromatograph(Lunan SP6890) equipped with a SE-54 capillary column and a FIDdetector. Analysis conditions were as follows: injection port tem-perature, 250C; detector temperature, 250C; oven temperatureprogram, 60C, hold for 2 min, 50-220C at a 15C/min gradient,hold for 10 min. The liquid mixture consisted of PO, propylene car-bonate (PC), and diol as the possible byproduct originating fromthe hydrolysis of epoxide with trace H2O. The carbon balance wasnearly 100%. The conversion of PO and selectivity to PC was cal-culated on the ground of an area-normalization method. |
99% | With tri-n-butyl(2-hydroxyethyl)phosphonium iodide at 90℃; for 3h; Autoclave; | |
99% | With L-glutamatozinc dihydrate; tetrabutylammonium bromide at 80℃; for 6h; Autoclave; | |
99.1% | With coordinatively unsaturated metal based ionic liquid N(n-Bu)3Br at 80℃; for 8h; | |
99.3% | With [carboxy functionalised bis ammonium immobilized on polystyrenes]Br2 In neat (no solvent) at 130℃; for 2.5h; Autoclave; Green chemistry; | |
99% | With ethylenediaminetetraacetic acid; tetrabutylammonium bromide at 70℃; for 18h; Autoclave; | 1 2.2. General procedure for the cycloaddition reaction of epoxidesand CO2 General procedure: The cycloaddition reaction of epoxides and CO2was conductedin a stainless steel autoclave (50 mL inner volumes). In a typicalreaction, the reactor was charged with EDTA (73.1 mg, 0.25 mmol),TBAB (80.6 mg, 0.25 mmol) and styrene oxide (0.6008 g, 5 mmol)successively at room temperature. Then, CO2was introduced intothe reactor and pressure was adjusted to 5 bar at 70C. The auto-clave was heated at this temperature for 18 h, and the pressurewas kept constant during the reaction. After the reaction was com-pleted, the reactor was cooled to 0C in ice-water bath, and thenthe excess of CO2was carefully vented. An aliquot of the samplewas taken from the resultant mixture and dissolved in ethyl acetatefor1H NMR analysis. The conversion of epoxide and yield of cycliccarbonate were determined by 1,3,5-trimethyoxybenzene as theinternal standard in CDCl3. The residue was purified by columnchromatography with ethyl acetate-petroleum ether as the eluentto afford the desired product. Spectral data for the products (2a-f)are as follows: |
99.9% | With [5,15-di(3-((8-1H-imidazol-1-yloctyl)oxy)phenyl)porphyrin]cobalt(III) chloride 3/2 dichloromethane solvate In neat (no solvent) at 120℃; for 6h; Autoclave; Green chemistry; | |
99% | With C8H10Cl2Co2N2O4; N,N,N-tributyl-1-butanaminium iodide In neat (no solvent) at 75℃; for 6h; Autoclave; Inert atmosphere; Sealed tube; | |
99% | With poly-carboxylic acid quaternary phosphine at 150℃; for 4h; Autoclave; | 3 Example 3 into the 75mL equipped with a magnetic stainless steel autoclave were added 10mg of poly-carboxylic acid quaternary phosphine catalyst and ionic liquid nano 14.3mmolpropylene oxide using electric furnace heated to 150 , again introduced into the reactor 2.0MPaCO2gas, reaction after 4h, the autoclave pressureforce is no longer declining, the reaction was stopped, cooled to room temperature, the autoclave was opened and allowed to slowly return to room temperature; Finally, add internal standard inline into the autoclavebenzene, use Agilent gas chromatography detection 6820GCTCD quantitative analysis is performed to obtain a yield of 99.0% propylene carbonate, selected fromselective 99.9%. |
99% | With 1,8-Octanediol; C24H19CoF3N3O4; tetra-n-butyl-ammonium chloride at 20 - 100℃; for 16h; Autoclave; | 1-1-5 Synthesis of cyclic propylene carbonate using the complex [Cr (babhq) OC (O) CF 3] from Example 1-1 in the presence of TBACl and 1,8-octanediol Cr (III) catalyst [Cr (babhq) OC (O) CF3] (10.6 mg, 0.020 mmol)Tetrabutylammonium chloride (TBAC1, 24.0 mg, 0.086 mmol),A solution of 1,8-octanediol (126 mg, 0.862 mmol)And propylene oxide (9.4 mL, 133 mmol)Was charged in a 160 mL autoclave equipped with a hollow shaft stirrer,(20 bar) at room temperature (propylene oxide / catalyst / TBACl molar ratio = 4304/1 / 4.1).The reaction mixture was then heated to & lt; RTI ID = 0.0 & gt; 100 C & (Over a period of 10 minutes)And stirred at 700 rpm for 16 hours.The autoclave was then cooled to 15 under the aid of an ice bath and the excess CO2 excess pressure was slowly released. After opening the autoclave, an NMR sample was taken for quantitative analysis and measured in CDCl3. |
99% | With caesium bromide In methanol at 20 - 99.84℃; for 8h; Autoclave; Industrial scale; | 6.a Embodiment 1 the 200 ml in the high-pressure reactor, adding cesium bromide 0.5mmol, methanol 20mmol, epoxy propane 40mmol, closed high-pressure reactor, is charged with an appropriate amount of carbon dioxide at room temperature, heating high-pressure reaction kettle until 373K, the carbon dioxide pressure to 1.0 MPa, the constant temperature reaction 8h, the high-pressure autoclave after the reaction cooling to normal temperature, opening the purge valve slowly to atmospheric pressure, the reactor is opened, gas chromatographic analysis of the reaction liquid, the propylene carbonate ester production rate 99%, the selectivity 99%. |
99% | With tetrabutylammonium bromide at 40℃; for 1h; Autoclave; Industrial scale; | |
99% | With aluminium porphyrin porouscomplex at 100℃; for 2h; Autoclave; | 1 To a 10 mL stainless steel autoclave, 6.010 10_4 mmol of catalyst (in the general formula (I) A1, Ri and R2 are both H), 12 mmol epoxy propane and 0.12 mmol cocatalyst (R3 in formula (II) is n-butyl, Y is Br), carbon dioxide is fed to an initial pressure of 3.0 MPa, After stirring for 2 hours at a temperature of 100 ° C, the mixture was quickly cooled to room temperature in cold water and then cooled in ice water. After slowly releasing the remaining carbon dioxide, the catalyst was separated by filtration, and the appropriate filtrate was subjected to gas chromatography analysis. The yield of the obtained cyclic carbonate was 99%. At the initial stage of the reaction, the T0F value was as high as 15000 h- |
99% | With C58H92AlClN6O16(2+)*2Br(1-) In neat (no solvent) at 50℃; for 2h; Autoclave; | |
99.2% | With tetrabutylammonium bromide at 100℃; for 1h; | |
99% | With aluminum porphyrin-based ionic porous organic polymer at 25℃; for 8h; Autoclave; | |
99.8% | With chlormethylated styrene resin supported tris-(2,4,6-trimethoxyphenyl)phosphine bromide at 120℃; for 0.5h; Autoclave; | 17 Example 17 General procedure: In a 100 ml stainless steel autoclave, Chlormethylated styrene resin loaded tris (2,4,6-trimethoxyphenyl) phosphine (X = Br in the formula) 0.24 g (0.2 mmol calculated as tris (2,4,6-trimethoxyphenyl) phosphine) 2 ml of propylene oxide (1a) (41.5 mmol), Sealed reactor, Filled with 1.5MPa pressure of carbon dioxide, Controlled by the temperature controller temperature slowly rose to 120 , The reaction time is 2.5h. After the reaction was completed, the autoclave was cooled to -15 ° C, Excessive release of carbon dioxide slowly, After filtering off the catalyst, The resulting product (2a) was subjected to gas chromatographic analysis, Selectivity 99.8%, yield 99.7%.As in Example 1, The catalyst was used in an amount of 2.5 g (2.075 mmol in terms of tris (2,4,6-trimethoxyphenyl) phosphine) over a period of 0.5 h, Other conditions remain unchanged, The product (2a) selectivity of 99.8% Yield 99.8%. |
99.6% | With poly(N,N'-(methylene)bis(N,N-dimethyl-1-(4-vinylphenyl)methanaminium) chloride) In neat (no solvent) at 90℃; for 6h; Autoclave; | |
99% | With 1-aminopyridinium iodide modified [In2(diphenate)3(1,10-phenanthroline)2] In ethanol; lithium hydroxide monohydrate for 0.166667h; Microwave irradiation; | |
99% | With functionalised polyphenolic ionic polymers In neat (no solvent) at 80℃; for 10h; Autoclave; | |
99% | With tetrabutylammonium bromide In neat (no solvent) at 40℃; for 8h; | |
99% | With UiO-66/SnS2 nanocomposite In neat (no solvent) at 120℃; for 12h; Green chemistry; | |
99% | With 2-(bis(5-(tert-butyl)-2-hydroxybenzyl)amino)-N,N,N-trimethylethan-1-aminium iodide In dimethyl sulfoxide at 20℃; for 12h; Inert atmosphere; Schlenk technique; | |
99.1% | With choline chloride-PEG600 deep eutectic solvents In neat (no solvent) at 150℃; for 5h; Autoclave; | |
99% | With tetrabutylammonium bromide at 100℃; for 1h; Autoclave; | |
99.2% | With 1,1,1,3',3',3'-hexafluoro-propanol; N,N,N-tributyl-1-butanaminium iodide at 103℃; for 1h; Autoclave; | The reactions were performed in a stainless steel pressure reactor (volume 200 mL) equipped with sensors for recording the temperature and pressure at 1-min steps. The reactor was loaded with the catalyst components, closed, and evacuated, after which propylene oxide was loaded through a vent from a measuring tank and CO2 was fed until a required pressure had been reached and then the gas inlet vent was closed and stirring and heating were initiated. After completion of the process (pressure drop is no longer observed), the reactor was cooled down, unreacted propylene oxide was removed in a water-jet pump vacuum, and the residue was taken out and subjected to vacuum distillation to isolate propylene carbonate, bp 82-84 °C (3 mmHg) {bp 241.7 °C (760 mmHg) [19]. The purity of the product was no less than 99% (1H NMR data), nD 1.4209 (nD20 1.4209 [19]). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.37 d (3H, CH3, 3J 6.1 Hz), 4.06 m (1H, CH2, 2J ≈ 3J = 7.3-8.6 Hz), 4.57 t (1H, CH2, 2J ≈ 3J = 7.9-8.6 Hz), 4.89 m (1H, CH). |
99% | With 2Dy(3+)*2Zn(2+)*4C26H32N2O4(2-)*2C2H3O2(1-)*5CH4O*H2O; tetrabutylammonium bromide In neat (no solvent) at 120℃; for 1h; Autoclave; | |
99% | With tetrabutylammonium bromide at 25℃; for 48h; Autoclave; | 2.3. Cycloaddition reaction General procedure: CTF-CSUs catalyst (10 mg), TBAB (1 mmol) and the correspondingepoxide (10 mmol) were added to a 25 mL stainlesssteel reactor equipped with a magnetic stirring bar and pressurecontroller. The vessel was pressurized with CO2 (0.1 MPa). Afterstirring for 48 h at 25 °C, the reaction mixture was filtered offand washed with CH2Cl2 to ensure complete removal of the productand any unreacted starting materials from the pores of theCTF-CSUs organocatalyst. The filtrate was concentrated and thecrude samples were analyzed by 1H NMR spectroscopy. To measurethe recyclability, the separated powder catalyst was continuouslyrecovered by centrifugation, washing withdichloromethane, desiccation. Finally, the catalyst was used againfor the subsequent cycle operation with fresh reactants under thesame reaction conditions. |
99% | With poly(4-vinylpyridine)supported iodine In neat (no solvent) at 100℃; for 2h; Green chemistry; chemoselective reaction; | |
99.8% | With ionic liquid polymer 1 at 110℃; for 3h; Autoclave; | 1 143 mmol of propylene oxide and 300 mg of ionic liquid polymer 1 powder having a particle diameter of 100 mm were placed in a 750 mL closed reaction vessel and mixed uniformly.The temperature of the reaction vessel was maintained at 110 ° C, and carbon dioxide gas was continuously supplied into the reaction vessel to maintain the pressure of the reaction system in the autoclave at 2 MPa.The addition reaction was carried out for 3 hours to obtain a product of propylene carbonate, and the yield of propylene carbonate was 99.8 mol%. |
99% | With bis(trifluoromethylsulfonyl)imide imidazolium ionic liquid immobilized on periodic mesoporous organosilica In neat (no solvent) at 90℃; for 1h; Sealed tube; Green chemistry; | |
99% | With (C36H52O2N2)AlCl; tetrabutylammonium bromide at 150℃; for 0.0135556h; Flow reactor; | |
99% | With C24H25N4O3(1+)*I(1-); 1,8-diazabicyclo[5.4.0]undec-7-ene at 90℃; | |
99% | With 1-(3-bromopropyl)-3-methyl-1H-imidazol-3-ium functionalized covalent organic framework containing 2-hydroxybenzene-1,4-dialdehyde and 1,3,5-tris(4-aminophenyl)benzene at 100℃; for 48h; Sealed tube; | |
99% | With Mo12O40PH3Zn4*3C12H10N2; tetrabutylammonium bromide at 45℃; for 10h; | |
99.4% | With potassium iodide; lignin at 80℃; for 10h; Autoclave; Enzymatic reaction; | 1-20 Example 1 method of execution: In a 50mL stainless steel autoclave, add alkaline lignin 0.0266g(The amount of active hydroxyl groups is 0.1 mmol), KI 0.0169 g (0.1 mmol), propylene oxide(1a) 1 mL (15 mmol), sealed reactor, charged with carbon dioxide at a pressure of 1.0 MPa,The kettle was slowly heated to 80 ° C for a reaction time of 10 h.After the reaction was completed, the reaction vessel was cooled to room temperature, and ethyl acetate was used as an absorption liquid.Excessive carbon dioxide is slowly released. After separating the catalyst by filtration,The obtained product (2a) was subjected to gas chromatography analysis with a selectivity of 99.4% and a yield of 94.5%. |
99% | With ionic liquid immobilized cobalt-doped ZIF-8(Zn) at 100℃; for 2h; Schlenk technique; | |
99% | With 2C8H15N2(1+)*Br4Zn(2-) at 25℃; for 5h; | |
99% | With tetrabutylammonium bromide; 2Cu(2+)*4I(1-)*4C6H5N2O2(1-)*4C3H7NO*4Cu(1+) at 80℃; for 8h; | |
99% | With (2-hydroxyphenyl)diphenyl(propyl)phosphonium iodide immobilized on plasma generated amorphous hydrogenated carbon thin film coated on silica at 45℃; for 6h; Autoclave; | |
99.9% | With tetrabutylammonium bromide at 60℃; for 4h; | |
99% | With C3H7NO*H2O*3C17H7O7(3-)*4Zn(2+) at 20℃; for 48h; | 1-3; 1 Comparative example 3 Using Cu2+ coordinated Cu(tactmb) metal-organic framework material (MOF), under normal temperature and pressure conditions, test the substrate conversion rate when catalytic CO2 reacts with propylene oxide to produce propylene carbonate, and implement it The complexes obtained in Example 1 were compared. The complexes obtained in Comparative Examples 1-3 and Example 1, under the same conditions, tested the substrate conversion rate when each group catalyzed the reaction of CO2 and propylene oxide to produce propylene carbonate under normal temperature and pressure; The reaction time is 48h, and the test results are shown in the following table and Figure 5. |
99% | With Ni(1,4-bis(4-pyrazolato)benzene); tetrabutylammonium bromide In neat (no solvent) at 80℃; for 24h; | |
99% | With tetrabutylammonium bromide at 90℃; for 24h; | |
99% | With tetrabutylammonium bromide; C17H8F6O4(2-)*Zn(2+)*C3H6N6 at 20℃; for 24h; | |
99% | With polymerized ionic liquid 1 at 120℃; for 3h; | 1-11 Reaction process: In a 15mL closed reactor,Add 0.83g of propylene oxide and 150mg with a particle size of 100μmOf polymeric ionic liquid 1The powder is mixed uniformly, and the temperature of the reactor is maintained at 120°C,Carbon dioxide gas is continuously introduced into the reactor,Maintain the pressure of the reaction system in the kettle at 2MPa, and carry out the addition reaction for 3h,The product propylene carbonate was obtained, and the yield of propylene carbonate was 99%. |
99% | With tetrabutylammonium bromide at 60℃; for 12h; | |
99% | With poly[[[triaqualanthanum(III)]-μ-5-sulfonatoisophthalato] monohydrate]; tetrabutylammonium bromide In acetonitrile at 20℃; for 1h; Autoclave; | |
99% | With C20H28N3S(1+)*I(1-) at 120℃; for 20h; Autoclave; | 1-8 Application example 1-13: Using catalyst 1-5 to catalyze the ring opening of alkylene oxide to generate cyclic carbonate General procedure: Take the catalyst (0.07mmol) prepared in Example 1-5 and add it to the autoclave,And add 35mmol of alkylene oxide, charge 1.2MPa CO2,And react for 20h at a given temperature. And then release carbon dioxide,Take the reaction liquid to measure the nuclear magnetic field to characterize the conversion rate of the monomer. |
99% | With C11H18BrN4Zn(1+)*Br(1-) at 125℃; for 3h; Inert atmosphere; Autoclave; | |
99% | With tetrabutylammonium bromide; C47H53Cl2N2O4Sm*C4H8O In neat (no solvent) at 70℃; for 24h; | |
99% | With glacial acetic acid; potassium iodide at 90℃; for 1h; Autoclave; | 1-22 Example 1 Add 226μL (3.95mmol) of acetic acid, 683mg (4.1mmol) of potassium iodide, 3.6mL (51.4mmol) of propylene oxide to a 100mL autoclave, and quickly close the reactor, then raise the temperature of the reactor to 90, and then The reactor was filled with 0.9MPa CO2gasat one time, and the reaction was stirred at a constant temperature for 30 minutes; after the reaction, the reactor was placed in liquid nitrogen to cool, and the excess CO2was slowly released. The reactor was opened, and the liquid was analyzed by nuclear magnetism. The yield of propylene carbonate is 98.13%, and the selectivity is 100%. |
99.1% | With C15H18N4OP(1+)*Br(1-) at 130℃; for 1h; Autoclave; | 13-17; 5-6 General procedure: (1) In a 100mL stainless steel autoclave,Add the catalysts in the amounts shown in Examples 1 to 29 in Tables 1 to 3.(2) Pass the epoxy compound 1M shown in Examples 1 to 29 in Tables 1 to 3 into the stainless steel autoclave;(3) Airtight the reactor, flush with carbon dioxide, and keep the system pressure at about 1.0MPa;(4) The reaction gas is heated, and the temperature is controlled by a temperature controller to slowly rise, and the final temperature is controlled at 130°C;(5) Afterwards, control the pressure of carbon dioxide to 2.0Mpa;(6) After reacting for 1 hour, cool to room temperature, unload the reaction kettle, absorb excess carbon dioxide with saturated sodium carbonate solution, and distill the resulting liquid under reduced pressure to obtain the product cyclic carbonate. |
99.2% | With biphenyl at 100℃; for 3h; Autoclave; | 17 General procedure: In a 60mL stainless steel autoclave, add the catalyst PS-[Py-p-NHCOCH2O(CH2CH2O)12CH2CONH-p-Py(n-C4H9)][2Cl], 10.5mmol styrene oxide (R2=Ph, R3=H), PS-[Py-p-NHCOCH2O(CH2CH2O)12CH2CONH-p-Py(n-C4H9)][2Cl]/SO=1/100(mol/mol), and the internal standard biphenyl, stirred for 2h at a CO2 pressure of 0.8 MPa and a reaction temperature of 120 °C, after the reaction is over, the liquid phase enters the GC and uses the internal standard method for quantitative analysis. The SO conversion rate is 96.5%, the selectivity is 99%, the yield of cyclic carbonate is 95.5%, and the initial TOF value is 63 h-1 when the reaction is 0.5h. |
99.3% | With C34H19O8(3-)*Ce(3+); N,N,N,N-tetramethylammonium bromide In 1,2-dimethoxyethane at 100℃; for 12h; Autoclave; | |
99.9% | With Zn(betaine)<SUB>2</SUB>Br<SUB>2</SUB>; 1-methyl-3-hexylimidazolium tetrafluoroborate at 40℃; for 6h; Sealed tube; Green chemistry; | |
99% | With metalloporphyrin-based porous ionic polymer catalyst at 100℃; for 5h; Autoclave; High pressure; Sealed tube; | 2.3. The general procedure for cycloaddition of CO2 with PO All the cycloaddition reactions were conducted in a 10 mL stainlesssteel autoclave equipped with an oil bath magnetic stirrer. Generally,the accurately weighed catalyst ZnPro-PiP and propylene oxide (PO)were added to the autoclave, followed by slowly purging with CO2.Subsequently, the reactor was sealed and charged with 1.0 MPa CO2 atroom temperature. Then, the reactor was put into the stirrer at settemperature (100 C) for 5 h. After cooling to room temperature, theautoclave was further cooled with ice water, followed by the slow release of the excess CO2. The mixture was filtered to select the solidcatalyst ZnPro-PiP that then recovered by wash with methanol andvacuum drying method. The filtrate was diluted with ethyl acetate andanalyzed by gas chromatography to determine the PC yield. All the resultsare averaged by two runs. 1HNMR and 13C NMR spectroscopy werealso used for confirming the PC product. |
99% | With tetrabutylammonium bromide at 90℃; for 3h; Autoclave; | 2.4. CO2 and epoxides coupling reaction General procedure: A 20-ml autoclave with a magnetic stirrer was first dried in an ovenat 110 C overnight. The autoclave was naturally cooled down to roomtemperature. After the addition of catalyst (1 mg), TBAB (0.5 mmol),and epoxide (25 mmol) without any additional solvents, the autoclavewas pressurized with 1 MPa of CO2. The autoclave was put in an oil bath,and the reaction was carried out for 3 h at 90 °C with rapid stirring at400 rpm. After completion of the reaction, the autoclave was placed inan ice bath to cool. And the pressure was released. The catalysts wereseparated by centrifugation, and a small quantity of the reaction mixturewas collected for 1H NMR analysis to calculate the reaction conversion.Pure cyclic carbonates were isolated by distillation or column chromatography.The reusability of the catalyst was tested after successive reactionrounds of CO2 and PO coupling. The crude product containing therecovered catalyst was centrifuged at 12,000 rpm. The supernatantliquid was then separated. The remaining solid catalyst was collectedand washed several times with tert-BuOH and H2O to remove the catalystsurface substrate molecules thoroughly. The collected catalyst andTBAB were used for the subsequent reaction rounds in the same autoclaveunder the same reaction condition. The catalyst was recycled forsix reaction rounds. The CO2 coupling reactions with other commercialepoxides such as 1,2-butylene oxide, epichlorohydrin, tert-butyl glycidylether, styrene oxide, phenyl glycidyl ether were performed using thesimilar procedure described above. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: carbon dioxide With potassium carbonate In N,N-dimethyl-formamide at 30℃; for 4h; Stage #2: 1-bromo-2-propanol In N,N-dimethyl-formamide at 30℃; for 20h; | |
With tetraethylammonium perchlorate 1.) electrolysis, MeCN, 0 deg C, 2.) room temperature, 6 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | In N,N-dimethyl-formamide at 130℃; |
Yield | Reaction Conditions | Operation in experiment |
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With Co(III) salen-type In 1,2-dimethoxyethane at 25℃; for 3h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Co(III) salen-type In methanol; 1,2-dimethoxyethane at 25℃; for 20h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Co(III) salen-type In 1,2-dimethoxyethane at 25℃; for 48h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,2-propylene cyclic carbonate; 1,6-Hexanediamine In dichloromethane at 60℃; for 2h; Stage #2: With pyridinium chlorochromate In dichloromethane at 20℃; for 2h; | 9 Preparation of a Poly-N-Lactyl-N-hexamethylene-N'-hexamethyleneurea The first step of this preparation is the synthesis of 3,3'-hexamethylene-bis-(5-methyloxazolidine-2,4-dione) as described in the pending Italian patent filed by Chorisis srl. 10 mmoles of hexamethylenediamine and 20 mmoles of propylene carbonate are mixed and maintained at 60° C. for two hours. The adducts mixture thus formed is cooled and dissolved in 120 ml of methylene chloride, then treated at room temperature with 120 mmoles of pyridinium chlorochromate. The mixture is stirred for two hours at room temperature. The liquid is separated from the tarry residue and concentrated under reduced pressure. The residue is eluted with methylene chloride on a silica gel column. Fractions containing the product corresponding to formula 3, as detected by GC-MS and identified by 1H and 13C-NMR, are collected and dried. MS: 312 (M+, 7.5%), 241 (7.9%), 184 (37.4%), 170 (12.6%), 156 (5.6%), 143 (7.0%), 129 (3.3%), 116 (100.0%), 82 (44.9%); 1H-NMR: 5.1 (q, 2H), 3.4 (m, 4H), 1.6 (m, 4H), 1.5 (d, 6H), 1.3 (m, 4H); 13C-NMR: 174 (C=O), 156 (C=O), 76 (1H), 40 (2H), 27 (2H), 26 (2H), 16 (3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15.4% | at 100℃; | 1 Results on hydrolysis A PC-hydrolysis experiment has also been carried out with the Zn. Cr203 catalyst. The operation conditions were [100 °C,] 25 bar and a feed consisting of a PC: water mixture of 3: 1 molar ratio introduced at the higher space velocity of WHSV=5 g/g/h and a [N2] flow of 2.1 g/g/h. Under these conditions, the Zn. [CR203] catalyst allowed a MPG yield of 15.4 mole% without formation of side products in detectable amounts. Under enhanced aging condition at 160 [°C,] the leaching rate of zinc species amounted [TO-0.] 05 mg Zn/kg liquid product. For comparison, a blanc experiment ran with a SiC bed allowed an MPG yield of 0.2 mole% only under these conditions. Similar results are obtainable with the other zinc supported catalysts of the invention. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With [carbonylchlorohydrido{bis[2-(diphenylphosphinomethyl)ethyl]amino}ethylamino] ruthenium(II); potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 140℃; for 10h; Autoclave; | 11 Example 11 Hydrogenation of propylene carbonate catalyzed by ruthenium complex 1a In a glove box, into a 125 mL autoclave was charged with ruthenium complex 1a (3.5 mg, 0.057 mmol), potassium tert-butoxide (0.5 mg, 0.057 mmol), tetrahydrofuran (20 mL) and propylene carbonate (2.92 g, 28.6 mmol). The autoclave was sealed, removed from the glove box, and filled with hydrogen gas to 50 atm. The reaction vessel was heated in an oil bath at 140°C with stir for 10 hours. The reaction vessel was cooled in an ice-water bath for 1.5 hours, and the excess of hydrogen was slowly deflated. The conversion rate for the reaction was determined as 99% with p-xylene as internal standard by using gas chromatography. Both of the yields of methanol and ethylene glycol are 99%. |
92% | With potassium <i>tert</i>-butylate; hydrogen; C16H18BrCoINO2 In dibutyl ether at 160℃; for 20h; Sealed tube; Autoclave; | |
With water at 140℃; | 2 Example 2; An experiment was carried out which was similar to Example 1 but in which a higher weight hourly space velocity was applied. A mixture of water and propylene carbonate was contacted at 140 C and a nitrogen pressure of 25 x 105 N/m2 at a weight hourly space velocity of 15 gram feed/gram CATALYST/HOUR at a water to propylene carbonate molar ratio of 0.36 with a catalyst consisting of a mixture of magnesium and aluminium hydroxide having a molar ratio of 5 to 1. Further details both of the feed and of the product obtained are given in Table 2. The phosphonium catalyst was tributyl-methyl-phosphonium iodide. The feed did not contain 1,2-propanediol. |
With water at 140℃; | 2 Example 2; An experiment was carried out which was similar to Example 1 but in which a higher weight hourly space velocity was applied. A mixture of water and propylene carbonate was contacted at 140 C and a nitrogen pressure of 25 x 105 N/m2 at a weight hourly space velocity of 15 gram feed/gram CATALYST/HOUR at a water to propylene carbonate molar ratio of 0.36 with a catalyst consisting of a mixture of magnesium and aluminium hydroxide having a molar ratio of 5 to 1. Further details both of the feed and of the product obtained are given in Table 2. The phosphonium catalyst was tributyl-methyl-phosphonium iodide. The feed did not contain 1,2-propanediol. | |
In cyclic carbonate or alkylene glycol at 50 - 300℃; | ||
70 %Chromat. | With [carbonylchlorohydrido{bis[2-(diphenylphosphinomethyl)ethyl]amino}ethylamino] ruthenium(II); potassium <i>tert</i>-butylate; hydrogen In methanol at 100℃; for 2h; Schlenk technique; | |
96 %Chromat. | With water; N,N'-dimethylimidazolium-2-carboxylate at 140℃; for 1h; Autoclave; Sealed tube; | |
With [Ru(1,1,1-tris(diphenylphosphinomethyl)ethane)(trimethylenemethane)]; hydrogen; bis(trifluoromethanesulfonyl)amide In 1,4-dioxane at 140℃; for 16h; Autoclave; Inert atmosphere; | ||
With RuCl2[(Ph2PCH2CH2)2NH](t-Bu-NC); potassium <i>tert</i>-butylate; hydrogen at 120℃; for 12h; | 40 Example 40. Hydrogenation of propylene carbonate using RuCl2[(Ph2PCH2CH2)2NH](t-Bu-NC) as catalyst The catalyst (30 mg) is added to a mixture of propylene carbonate (3.0 g) and KO'Bu (10 mg) in a 100 ml Parr pressure reactor. The mixture was degassed with hydrogen and the pressure was set to 20 atm. The mixture was stirred for 12 hours at 120 °C. It was then cooled to room temperature. The NMR spectra of the reaction mixture showed 100% conversion of the ethylene carbonate to propylene glycol and methanol. | |
With water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: poly(propylene carbonate) With [1,3-bis(2,4,6-trimethylphenyl)imidazol]-2-ylidene In toluene at 20℃; for 0.166667h; Stage #2: With methanol In toluene at 80℃; for 3h; | 1 EXAMPLE 1 Depolymerization of Poly(propylene carbonate) (Mw=50,000) with isolated carbene: 7 mg (0.02 mmol) of 1,3-(2,4,6-trimethylphenyl)imidazol-2-ylidene dissolved in toluene (0.6 mL), was added to a stirred mixture of 0.5 g of poly(propylene carbonate) in toluene (10 mL), under N2. After stirring for 5 minutes at room temperature, 2 mL of methanol were added to the reaction mixture and the temperature was brought to 80° C. Stirring was continued for 3 hours followed by the evaporation of the solvent in vacuo. The 1H and 13C NMR spectra showed the presence of a single monomer, 4-methyl-[1,3]-dioxolan-2-one. However, there were 4 peaks in the GC-MS. GC-MS: a) m/z (5%) 5.099 min=106 (42), 103 (5), 91 (100), 77 (8), 65 (8), 51 (8) b) m/z (5%) 5.219 min=106 (60), 105 (30), 103 (8), 91 (100), 77 (8), 65 (5), 51 (5) c) m/z (85%) 6.750 min=102 (15), 87 (40), 58 (20), 57 (100). Major product. d) m/z (5%) 9.030 min=136(10), 135 (100), 134 (70), 120 (85), 117 (8), 103 (5), 91 (14), 77 (10), 65 (5). 1H NMR:1.4 (d, 31H), 3.9 (t, 1H), 4.5 (t, 1H), 4.8 (m, 1H). 13C NMR: 18.96, 70.42, 73.43, 154.88 | |
Stage #1: poly(propylene carbonate) With potassium <i>tert</i>-butylate; 1-ethyl-3-methyl-1H-imidazol-3-ium chloride In tetrahydrofuran at 20℃; for 0.166667h; Stage #2: With methanol In tetrahydrofuran at 20℃; for 3h; | 4 EXAMPLE 4 EXAMPLE 4 Depolymerization of poly(propylene carbonate) (Mw=50,000) with in-situ carbene: To a mixture of 7 mg (0.047 mmol) of 1-ethyl-3-methyl-1-H-imidazolium chloride in tetrahydrofuran (THF) was added 4 mg (0.038 mmol) of potassium t-butoxide (t-BOK), under N2.After 30 min stirring, 0.1 ML of the reaction mixture was transferred to a flask that was charged with 0.5 g of poly(propylene carbonate) in 10 ML of THF. The reaction mixture was stirred for 10 min at room temperature followed by the addition of 2 ML of methanol.Stirring was continued at room temperature for 3 hours.Solvent was removed and the 1H and 13C NMR spectra showed the presence of a single product, 4-methyl-[1,3]-dioxolan-2-one.However, before the removal of the solvent the GC-MS of the crude reaction mixture showed 6 different compounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
7 Example 7: Preparation of 2-Propenoic acid, 1,7, 14 (or 1,7, 15 or 2,7, 14) -trimethyl- 4,12-dioxo-3, 13-dioxa-5, 11-diazapentadecane-1, 15-diyl ester Example 7: Preparation of 2-Propenoic acid, 1,7, 14 (or 1,7, 15 or 2,7, 14) -trimethyl- 4,12-dioxo-3, 13-dioxa-5, 11-diazapentadecane-1, 15-diyl ester The starting hydroxyalkyl carbamate, obtained by reacting 2 moles of propylene carbonate with 1 mole OF 2-METHYL-1, 5 DIAMINOPENTANE, is commercially-available from King Industries Ltd. (K-flex UD-320-100). Acrylation of K-flex UD-320-100 by transesterification was performed using same equipment as in Example 1. The reaction mixture containing 288.6 g K-FLEX UD-320- 100 (0.85 moles), 1301 g (13 moles, equivalent ratio alkyl acrylate to hydroxyalkyl carbamate=7.6) ethyl acrylate, 1000 ppm on end product of BHT and 300 ppm on end product of PTZ was first dried by azeotropic distillation, as in Example 1. AFTER adding 25.5 g Tyzor TPT-20B (weight ratio of catalyst to the generated carbamoyloxy (meth) acrylate=0.07), the reaction mixture was maintained at 102-103°C and the ethanol generated was taken off overhead as a ethanol/ethyl acrylate azeotrope. The reaction was continued until a measure of the refractive index indicated that no more ethanol was present in the distillate. Reaction time was 10 hours. After a same work- up procedure as in Example 1, a low colored product (1.9 Gardner) with 92 % of the OH groups from the starting hydroxyalkylcarbamate being acrylated according 1H NMR, was obtained. In another experiment, glycerol was used instead of water to precipitate the catalyst. In that case, filtration time was decreased by a factor 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate; potassium iodide In propylene glycol at 150℃; for 2.5h; | 12 Example 12 A mixture of 1,4-bis(2',6'-dimethyl-4'-hydroxyanilino)anthraquinone (1.50 g, 3.13 mmol) (U.S. Pat. No. 3,918,976), potassium iodide (1.0 g), potassium carbonate (0.45 g), propylene carbonate (3.84 g, 37.6 mmol) and propylene glycol (15 ml) was stirred and heated at 150 C. for about 2.5 hours. The mixture was allowed to cool to room temperature and methanol (50 ml) was added followed by 50 ml of water. The product was collected by filtration, washed with water and dried in air (yield 1.6, 95% of theory). FDMS supported the following expected structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 93.4% 2: 0.3% | at 180℃; for 4h; Gas phase; | The experiments were carried out in a 60 ml Hastelloy C (Hastelloy is a trademark of Haynes International, Inc. ) autoclave reactor equipped with a heating jacket and a gas inlet, and stirred by means of a gas-dispersing propeller. Following placement of the evaluated catalyst into the reactor, 5 g (86 mmoles) of propylene oxide (PO) were added. The reactor was then sealed and carbon dioxide (CO2) was introduced to a total pressure of 20 x 105 N/M2 (bar). Then the reactor was heated to 180 °C under stirring. At 180 °C, the total reactor pressure was adjusted with CO2 to 50 x 105 N/m2 (bar). After 4 hours at the above-described conditions, the reactor was cooled down rapidly, allowed to decompress, and samples were taken. The yields in propylene carbonate (PC) and 1,2- propanediol (monopropyleneglycol, MPG) were determined by gas chromatography (GC) using decane as an external standard, and expressed as mole%, based on the amount of moles of converted propylene oxide. Catalyst decomposition to the corresponding phosphine oxide was determined using 31P-NMR, and is expressed as % of phosphorus atoms of the phosphonium compound that had decomposed to the phosphine oxide. The results of the examples are summarised in Table 1. It is clear that the tetrabutyl chloride catalyst is unstable at the demanding operating conditions. The tetraalkyl phosphonium bromides outperform the other catalysts used in terms of yields versus catalyst stability. Tetra-n-butyl phosphonium bromide shows the best overall performance. |
1: 92.7% 2: 0.5% | at 180℃; for 4h; Gas phase; | The experiments were carried out in a 60 ml Hastelloy C (Hastelloy is a trademark of Haynes International, Inc. ) autoclave reactor equipped with a heating jacket and a gas inlet, and stirred by means of a gas-dispersing propeller. Following placement of the evaluated catalyst into the reactor, 5 g (86 mmoles) of propylene oxide (PO) were added. The reactor was then sealed and carbon dioxide (CO2) was introduced to a total pressure of 20 x 105 N/M2 (bar). Then the reactor was heated to 180 °C under stirring. At 180 °C, the total reactor pressure was adjusted with CO2 to 50 x 105 N/m2 (bar). After 4 hours at the above-described conditions, the reactor was cooled down rapidly, allowed to decompress, and samples were taken. The yields in propylene carbonate (PC) and 1,2- propanediol (monopropyleneglycol, MPG) were determined by gas chromatography (GC) using decane as an external standard, and expressed as mole%, based on the amount of moles of converted propylene oxide. Catalyst decomposition to the corresponding phosphine oxide was determined using 31P-NMR, and is expressed as % of phosphorus atoms of the phosphonium compound that had decomposed to the phosphine oxide. The results of the examples are summarised in Table 1. It is clear that the tetrabutyl chloride catalyst is unstable at the demanding operating conditions. The tetraalkyl phosphonium bromides outperform the other catalysts used in terms of yields versus catalyst stability. Tetra-n-butyl phosphonium bromide shows the best overall performance. |
90% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; cellulose at 120℃; for 2h; Autoclave; Green chemistry; |
1: 75.1% 2: 0.3% | at 180℃; for 4h; Gas phase; | The experiments were carried out in a 60 ml Hastelloy C (Hastelloy is a trademark of Haynes International, Inc. ) autoclave reactor equipped with a heating jacket and a gas inlet, and stirred by means of a gas-dispersing propeller. Following placement of the evaluated catalyst into the reactor, 5 g (86 mmoles) of propylene oxide (PO) were added. The reactor was then sealed and carbon dioxide (CO2) was introduced to a total pressure of 20 x 105 N/M2 (bar). Then the reactor was heated to 180 °C under stirring. At 180 °C, the total reactor pressure was adjusted with CO2 to 50 x 105 N/m2 (bar). After 4 hours at the above-described conditions, the reactor was cooled down rapidly, allowed to decompress, and samples were taken. The yields in propylene carbonate (PC) and 1,2- propanediol (monopropyleneglycol, MPG) were determined by gas chromatography (GC) using decane as an external standard, and expressed as mole%, based on the amount of moles of converted propylene oxide. Catalyst decomposition to the corresponding phosphine oxide was determined using 31P-NMR, and is expressed as % of phosphorus atoms of the phosphonium compound that had decomposed to the phosphine oxide. The results of the examples are summarised in Table 1. It is clear that the tetrabutyl chloride catalyst is unstable at the demanding operating conditions. The tetraalkyl phosphonium bromides outperform the other catalysts used in terms of yields versus catalyst stability. Tetra-n-butyl phosphonium bromide shows the best overall performance. |
1: 72% 2: 0.4% | at 180℃; for 4h; Gas phase; | The experiments were carried out in a 60 ml Hastelloy C (Hastelloy is a trademark of Haynes International, Inc. ) autoclave reactor equipped with a heating jacket and a gas inlet, and stirred by means of a gas-dispersing propeller. Following placement of the evaluated catalyst into the reactor, 5 g (86 mmoles) of propylene oxide (PO) were added. The reactor was then sealed and carbon dioxide (CO2) was introduced to a total pressure of 20 x 105 N/M2 (bar). Then the reactor was heated to 180 °C under stirring. At 180 °C, the total reactor pressure was adjusted with CO2 to 50 x 105 N/m2 (bar). After 4 hours at the above-described conditions, the reactor was cooled down rapidly, allowed to decompress, and samples were taken. The yields in propylene carbonate (PC) and 1,2- propanediol (monopropyleneglycol, MPG) were determined by gas chromatography (GC) using decane as an external standard, and expressed as mole%, based on the amount of moles of converted propylene oxide. Catalyst decomposition to the corresponding phosphine oxide was determined using 31P-NMR, and is expressed as % of phosphorus atoms of the phosphonium compound that had decomposed to the phosphine oxide. The results of the examples are summarised in Table 1. It is clear that the tetrabutyl chloride catalyst is unstable at the demanding operating conditions. The tetraalkyl phosphonium bromides outperform the other catalysts used in terms of yields versus catalyst stability. Tetra-n-butyl phosphonium bromide shows the best overall performance. |
1: 70.3% 2: 0.2% | at 180℃; for 4h; Gas phase; | The experiments were carried out in a 60 ml Hastelloy C (Hastelloy is a trademark of Haynes International, Inc. ) autoclave reactor equipped with a heating jacket and a gas inlet, and stirred by means of a gas-dispersing propeller. Following placement of the evaluated catalyst into the reactor, 5 g (86 mmoles) of propylene oxide (PO) were added. The reactor was then sealed and carbon dioxide (CO2) was introduced to a total pressure of 20 x 105 N/M2 (bar). Then the reactor was heated to 180 °C under stirring. At 180 °C, the total reactor pressure was adjusted with CO2 to 50 x 105 N/m2 (bar). After 4 hours at the above-described conditions, the reactor was cooled down rapidly, allowed to decompress, and samples were taken. The yields in propylene carbonate (PC) and 1,2- propanediol (monopropyleneglycol, MPG) were determined by gas chromatography (GC) using decane as an external standard, and expressed as mole%, based on the amount of moles of converted propylene oxide. Catalyst decomposition to the corresponding phosphine oxide was determined using 31P-NMR, and is expressed as % of phosphorus atoms of the phosphonium compound that had decomposed to the phosphine oxide. The results of the examples are summarised in Table 1. It is clear that the tetrabutyl chloride catalyst is unstable at the demanding operating conditions. The tetraalkyl phosphonium bromides outperform the other catalysts used in terms of yields versus catalyst stability. Tetra-n-butyl phosphonium bromide shows the best overall performance. |
1: 64.8% 2: 0.3% | at 180℃; for 4h; Gas phase; | 2 The experiments were carried out in a 60 ml Hastelloy C (Hastelloy is a trademark of Haynes International, Inc. ) autoclave reactor equipped with a heating jacket and a gas inlet, and stirred by means of a gas-dispersing propeller. Following placement of the evaluated catalyst into the reactor, 5 g (86 mmoles) of propylene oxide (PO) were added. The reactor was then sealed and carbon dioxide (CO2) was introduced to a total pressure of 20 x 105 N/M2 (bar). Then the reactor was heated to 180 °C under stirring. At 180 °C, the total reactor pressure was adjusted with CO2 to 50 x 105 N/m2 (bar). After 4 hours at the above-described conditions, the reactor was cooled down rapidly, allowed to decompress, and samples were taken. The yields in propylene carbonate (PC) and 1,2- propanediol (monopropyleneglycol, MPG) were determined by gas chromatography (GC) using decane as an external standard, and expressed as mole%, based on the amount of moles of converted propylene oxide. Catalyst decomposition to the corresponding phosphine oxide was determined using 31P-NMR, and is expressed as % of phosphorus atoms of the phosphonium compound that had decomposed to the phosphine oxide. The results of the examples are summarised in Table 1. It is clear that the tetrabutyl chloride catalyst is unstable at the demanding operating conditions. The tetraalkyl phosphonium bromides outperform the other catalysts used in terms of yields versus catalyst stability. Tetra-n-butyl phosphonium bromide shows the best overall performance. |
60 %Chromat. | With C20H24ClCrN4(2+)*2Cl(1-); tetra-(n-butyl)ammonium iodide at 100℃; for 0.5h; Supercritical conditions; Autoclave; | |
With rhodium(III) chloride; hydrogen In dimethyl sulfoxide at 140℃; for 16.5h; Autoclave; | ||
81 %Chromat. | With bis(imidazolate-2-carboxyaldehyde)zinc(II) In neat (no solvent) at 120℃; for 8h; Autoclave; | |
With zinc(II) iodide at 140℃; for 6h; Autoclave; Overall yield = 89.5 %; | ||
With water In acetonitrile at 40℃; for 1h; Autoclave; | 9.2 (2) Preparation of propylene glycol and propylene carbonate Propylene oxide, water, CO2, the acetonitrile as a solvent and the titanium silicalite molecular sieve TS-1 prepared in the step (1) as a catalyst were fed into a high-pressure reactor, after mixing, the reaction was stirred at 40 °C for 1 hour. The molar ratio of propylene oxide to water is 1: 4: 5, the weight ratio of solvent to catalyst is 80: 1, the weight ratio of propylene oxide to catalyst is 2: 1, the pressure in the autoclave is controlled at 0.5 MPa. The resulting mixture was then filtered and the composition of the resulting liquid phase mixture was determined by gas chromatography and the propylene oxide conversion and propylene glycol and propylene carbonate selectivity were calculated and the results are listed in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.3% | With sodium methylate In methanol; water | 2 Example 2 Example 2 A 150 ml autoclave was charged with 27.8 g (0.470 moles) of propylamine and 16.0 g (0.157 moles) of propylene carbonate. Thereafter, 3.03 g of a 28% methanol solution of sodium methoxide (0.0157 moles) was added to the autoclave, and the resulting mixture was heated to a temperature of 95° to 105° C. for 3 hours with stirring. At that time, the internal pressure of the autoclave attained to 3 kgf/cm2. After the reaction was completed, the resulting reaction solution was cooled to 25° C., and 150 ml of water was added to the reaction solution. Then, the mixture was stirred for one hour. After the resulting crystals were filtered off and washed twice with 25 ml of water, the resulting white crystals were dried under reduced pressure to give 18.2 g (0.126 moles) of 1,3-dipropyl urea in a 80.3% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In ethanol; water; | EXAMPLE 12 7-(2-Hydroxypropoxy)xanthone-3-carboxylic acid Methyl 7-hydroxyxanthone-3-carboxylate (2.0 g), propylene carbonate (10.0 g) and <strong>[75-58-1]tetramethylammonium iodide</strong> (0.20 g) were heated together at 170 for 4 h. the cooled reaction mixture was then boiled under reflux with a solution of sodium hydroxide (6.0 g) in water (200 ml) and ethanol (200 ml) for 30 min. The solution was cooled, filtered, and acidified with excess dilute hydrochloric acid. The precipitated product was filtered off, washed with water, and recrystallized twice from 95% 2-butanone-5% water mixture to yield 7-(2-hydroxy-propoxy)xanthone-3-carboxylic acid m.p. 252-254 (structure confirmed by proton magnetic resonance spectroscopy). Found: C, 65.06%; H, 4.54%. C17 H14 O6 requires C, 64.96%; H, 4.49%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.3 - 81 %Chromat. | at 170℃; for 8h; | 7 This example describes the preparation of dibutyl carbonate from propylene carbonate and butanol. Propylene carbonate (1.02 g; 10 mmol), butanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 170° C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51.7% | With 1-butyl-3-methylimidazolium hydroxide at 30℃; | 2 Using a batch reactor, the reactor specifications for the 1000ml, [Bmim]OH alkaline ionic liquid as a catalyst. The molar ratio of raw material propylene carbonate to ethanol is 1:2, the amount of catalyst is 0.1% of the total mass of raw materials. The reaction temperature was 30 °C, the reaction pressure was 0.01 MPa and the stirring speed was 200 r/min. Adding propylene carbonate to the reaction kettle and heating to the reaction temperature. The alkaline ionic liquid is dissolved in ethanol, heated to the reaction temperature, and then the ethanol solution is added to the reaction vessel to carry out the reaction. After completion of the reaction, the mixture was analyzed by gas chromatography, and the conversion of propylene carbonate was 52.3% and the yield of diethyl carbonate was 51.7%. |
19% | at 140℃; for 6h; | |
10% | at 130℃; for 4h; Autoclave; | A A. Preparation of dialkyl carbonate; The following procedure was used to prepare diethyl carbonate (DEC) from the cyclic carbonate ethylene carbonate (eC) or propylene carbonate (pC) and ethanol (EtOH) at low catalyst concentrations. The reactions were performed in a temperature controlled multitube autoclave. Agitation was obtained by mechanical shaking of the autoclave. Sodium ethoxide (NaOEt) catalyst, ethanol and cyclic carbonate (eC or pC) were mixed in a sealed vial prior to heat treatment in the autoclave. The catalyst was added as a solution in ethanol (made from 250 mg of NaOEt and 100 g of EtOH) . After 4 hours of heat treatment, the vials were cooled down to 4 °C and samples of the reaction mixtures in the vials were analyzed by means of gas chromatography. Three different autoclave temperatures were investigated: 65, 120 and 130 0C. Target yields of 30% DEC from eC and 10% DEC from pC were set. The yield of DEC was calculated as the molar concentration of DEC at the end of the experiment divided by the molar concentration of cyclic carbonate (eC or pC) at the beginning of the experiment. EtOH was used in 4 times molar excess over the cyclic carbonate.It was determined which minimum catalyst concentration (in ppmw, based on total weight of the reaction mixture) was needed at each of said autoclave temperatures to achieve the above-mentioned target yields. These minimum catalyst concentrations are shown in the table below. |
79.4 - 92 %Chromat. | at 170℃; for 8h; | 5 This example describes the preparation of diethyl carbonate from propylene carbonate and ethanol. Propylene carbonate (1.02 g; 10 mmol), ethanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 170° C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2. |
With cerium(IV) oxide at 160℃; for 6h; | General procedure: Initially, a blank experiment without catalyst was carried outfor the transesterification of EC with CH3OH (entry 1, Table 2).The result reveals that the reaction can proceed with a minorconversion under such circumstance, affording an EC conver-sion of 18.0%. Wherein, the monoester, namely HEMC, accountsfor a large proportion in the products. After the introduction ofCeO2-com, the catalytic conversion is slightly enhanced (entry 2).Upon employing the CeO2-meso catalyst, the conversion increasesdrastically, together with a high selectivity (96.1%) to the targetmolecule, DMC. Additionally, the variation of catalytic perform-ances obtained over different mesoporous ceria sample has beenfound. As listed in entries 3-5, the catalytic activity of CeO2-mesodecreases monotonously with the increase of their correspondingcalcination temperatures, and the prominent activity is achievedover CeO2-meso-400 | |
83 %Chromat. | With cerium(IV) oxide at 160℃; for 6h; | 9 (1) High specific surface cerium oxide (180 m2 g-1) was dried in an oven at 80 ° C for 2 h.(2) 1.2 mmol of high specific surface cerium oxide was used to catalyze propylene carbonate (10 mmol)And ethanol (250 mmol);(3) in the high pressure reactor for propylene carbonate and ethanol transesterification reaction, 160 reaction 6h;(4) after the reaction,Centrifuging the catalyst,The product was analyzed by gas chromatography,The final conversion of propylene carbonate was 86%The selectivity of dimethyl carbonate was 97%The yield of dimethyl carbonate was 83%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62.5 - 74%Chromat. | Fe-Zn double metal cyanide catalyst; at 170℃; for 8.0h; | This example describes the preparation of dihexyl carbonate from propylene carbonate and hexanol. Propylene carbonate (1.02 g; 10 mmol), hexanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 170 C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | at 90℃; for 3h; | 2 Secondary alcoholysis: The filtrate obtained in step (1) is fed into a rectifier with a reflux condenser, Adding methanol and a second catalyst in a ratio of 5: 3: 1 in terms of the molar ratio of the filtrate, the methanol and the second catalyst,In the stirring state, the reaction was carried out at 90°C for 3h, and the polyol fraction was collected at the top of the column. Said second catalyst being a composite of zinc oxide and lanthanum titanate in a mass ratio of 5:2; The dimethyl carbonate obtained by the above method has been tested,Its yield is greater than 93%. |
74% | With calcined hollow titanium silicon molecular sieve modified with sodium carbonate and ammonium dihydrogen phosphate In water at 100℃; for 8h; Autoclave; | 10 Weigh 1.0 g of anhydrous sodium carbonate and 0.3 g of ammonium dihydrogen phosphate, dissolved in 20.0 ml of water; After the solution was heated to 50 ° C, 10 g of HTS was added; At 600r. min-1 at a stirring rate for 4 h, Through the microwave drying quickly evaporate the water; The HTS modified with sodium carbonate and ammonium dihydrogen phosphate was then calcined at 550 ° C for 3 h; Finally, the calcined modified HTS was ground to 100 to 300 mesh. 15.2 g of propylene carbonate and 47.6 g of methanol were added to a stainless steel pressure vessel, Add 0.6g of the above catalyst; the stainless steel pressure reactor sealed, At 400r. min-1, the temperature was raised to 100 ° C and reacted for 8 h. After the reaction is complete, the sample is transferred to the distillation column by sampling analysis. As a result, the conversion of propylene carbonate was 74.3% The selectivity of dimethyl carbonate was 99.6% and the yield of dimethyl carbonate was 74.0%. |
74.7% | With tetramethylguanimidazole salt at 68℃; for 0.5h; | 5 In the belt reflux,In a stirred four-necked flask,Add PC1mol,Methanol 10mol,Catalyst [BTMG] IM joinedThe amount is 0.5%,The reaction temperature is 68°C,After 30 minutes of reaction, samples were taken for analysis.The amount of catalyst [TMG] IM added is 0.7%,Others are the same as in Example 1. |
35% | at 140℃; for 6h; | |
53.3 - 100 %Chromat. | at 70 - 180℃; for 8h; | 2; 3; 4; 10 This example describes the preparation of dimethyl carbonate from propylene carbonate and methanol. Propylene carbonate (1.02 g; 10 mmol), methanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 170° C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. Then, the excess, unreacted alcohol was removed from the reaction mixture by distillation. The products were isolated by column chromatography (using petroleum ether: dichloromethane=1:1 and then with dichloromethane : methanol=95:5). The products were also analyzed by gas chromatography and identified by 1H NMR, FT-IR and GC-MS. Results are tabulated in table-2.; This example describes the preparation of dimethyl carbonate from propylene carbonate and methanol over Fe-Zn double metal cyanide catalyst at 140° C. Propylene carbonate (1.02 g; 10 mmol), methanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 170° C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2.; This example describes the preparation of dimethyl carbonate from propylene carbonate and methanol over Fe-Zn double metal cyanide catalyst at 180° C. Propylene carbonate (1.02 g; 10 mmol), methanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 180° C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was separated by filtration from the reaction mixture. The products were isolated and analyzed as described in EXAMPLE 2. Results are tabulated in table-2.; This example describes the preparation of dimethyl carbonate from propylene carbonate and methanol over used (in 5 recycling experiments) Fe-Zn double metal cyanide catalyst. Propylene carbonate (1.02 g; 10 mmol), methanol (100 mmol), catalyst (250 mg) were charged in a 100 ml stainless steal autoclave having a Teflon-liner. The autoclave was closed and then placed in a rotating synthesis reactor (Hiro Co., Japan, Model-KH 02, rotating speed=30 rpm). The reaction was conducted at 70° C. for 8 h. The contents were allowed to cool to room temperature. Catalyst was eparated by filtration from the reaction mixture. The products were isolated and nalyzed as described in EXAMPLE 2. |
at 150℃; for 2h; | ||
With cerium(IV) oxide at 160℃; for 6h; | General procedure: The transesterification reactions of EC with CH3OH were carriedout in 80 mL stainless steel autoclave equipped with a magnetic stirrer. 25 mmol of EC and 250 mmol of CH3OH were mixed well,followed by the introduction of 0.1 g of the catalyst. The reactor was pressurized with CO2to 0.6 MPa and heated to 140C understirring for 2 h. After the reaction, the autoclave was cooled downin ice water and the mixture was centrifuged and analyzed by aGC equipped with a PEG-2000 capillary column coupled with a FIDdetector. The quantity of reagents and products are calculated byan area-normalization method. The carbon balance was 100 ± 5%. Inthe transesterification of EC with CH3OH, DMC and 2-hydroxyethylmethyl carbonate (HEMC) is the target molecule and by-product,respectively. The glycol is co-product. | |
31.4 mol | at 80℃; for 6h; Autoclave; | Reaction procedure EC (10 mmol), alcohol (100 mmol), and catalyst (5 wt% of EC) were taken in a Teflon-lined stainless-steel autoclave placed in a rotating hydrothermal reactor (Hiro Co., Japan; rotation speed = 50 rpm). Reactions were conducted at 40-100°C for 0.5-6 h. After completion of the reaction, the autoclave was cooled to 25°C, and the catalyst was separated by centrifugation/filtration. The liquid product was analyzed and quantified by gas chromatography (GC, Varian 3800; CP-SIL 5 column; 50 m × 0.25 mm × 0.25 m). The influence of reaction parameters (reaction time, reaction temperature, catalyst amount, and type of alcohol) on product yield was investigated. For comparison, experiments were also conducted with PC instead of EC. Those runs were carried out at 80-170°C. |
With (CeO2)0.85(La2O3)015 at 130℃; for 2h; Autoclave; Inert atmosphere; | 2.3. Synthesis of DMC from PropyleneCarbonate and Methanol Catalytic performance test for the synthesis of DMC frompropylene carbonate and methanol was conducted in a stainless steel autoclave batch reactor (200 ml) under nitrogenatmosphere. 0.7 g of catalyst, 5.3 ml of propylenecarbonate, and 20.1 ml of methanol were charged intothe reactor. Molar ratio of methanol to propylene carbonatewas fixed at 8. Reactor was then pressurized to 8 barusing N2, and the catalytic reaction was carried at 130 Cfor 2 h. Stirring speed was maintained at 400 rpm inorder to avoid mass transfer limitation. After the reaction,products were analyzed using a gas chromatograph (HP5890 II) equipped with a flame ionization detector (FID).HP-5MS capillary column was used for product separation.Yield for DMC was calculated as the ratio of molesof DMC produced with respect to moles of propylene carbonateconsumed. | |
66 %Chromat. | With cerium(IV) oxide at 160℃; for 6h; | 6 (1) The high specific surface cerium oxide (180 m2 g-1) was dried in an oven at 80 ° C for 1 h;(2) 0.6 mmol of high specific surface cerium oxide was used to catalyze propylene carbonate (25 mmol)And methanol (250 mmol);(3) in the high pressure reactor for propylene carbonate and methanol transesterification reaction, 160 reaction 6h;(4) after the reaction, the catalyst was separated by centrifugation, the product was analyzed by gas chromatography, the final propylene carbonateThe conversion was 66%, the selectivity of dimethyl carbonate was 99%, and the yield of dimethyl carbonate was 66%. |
With sodium methylate at 65 - 95℃; | 1 The following is an example of producing DMC using the process illustrated in FIG. 2. As illustrated in FIG. 2, carbon dioxide and ammonia were fed into urea synthesis device 101 and dehydrated to produce melt urea. The melt urea so generated and PG were fed into an alcoholysis reactor 110 at molar ratio2: 1 together with an alcoholysis catalyst to produce PC and ammonia. The alcoholysis catalyst used was a solid complex catalyst comprising at least two metal oxides, wherein the metals were selected from the group consisting of copper, zinc, magnesium, aluminum, iron, zirconium, and titanium (produced by Yashentech Corporation) . The alcoholysis catalyst is present at around 0.31.0 (wt). The alcoholysis reactor 110 used was a continuous feed tank reactor. The range of the alcoholysis reactor temperature was from 130 to 170 . The pressure of the alcoholysis reactor 110 was within 2040kPa. Under conditions described above, PG and urea reacted in the presence of alcoholysis catalyst to generate PC and ammonia. The ammonia generated was treated via a purification device 120 to remove impurities. Purified ammonia was used to react with CO2 in the urea synthesis device 101 to produce urea, thus forming recycled use of ammonia. The effluent of the alcoholysis reaction 110 contained PC, PG and alcoholysis catalyst. The effluent was then treated with a catalyst-separating device 130 to separate the alcoholysis catalyst. The recovery rate of the alcoholysis catalyst is more than 99.9, and wet content of the alcoholysis catalyst was less than 50. The effluent of the alcoholysis reaction was further treated with a vacuum distillation tower 141 to separate the PC and PG. The PG separated was reused in the alcoholysis reaction in the alcoholysis reactor 110. The PC-containing effluent of the vacuum distillation tower 141 was treated with a vacuum distillation tower 142, and a vacuum distillation tower 143 to obtain PC. The PC obtained was fed to a transesterification reactor 150 to react with methanol in the presence of a transesterification catalyst. The transesterification reactor 150 was a catalytic distillation tower reactor. The molar ratio of methanol to PC in the transesterification reaction was around 10: 1 to around 25: 1. The transesterification catalyst was NaOCH3. The transesterification catalyst was present at around 0.3 1.2 (wt) . The reaction condition of the transesterification reactor 150 was as follows: atmospheric pressure temperature for the bottom of the tower was from 75 to 95 temperature at the top of the tower was from 65 to 70 . The effluent from the bottom of the transesterification reactor 150 contained methanol, PG and transesterification catalyst the effluent from the top of the tower was an azeotrope comprising methanol and DMC. The effluent from the bottom of the transesterification reactor 150 was treated with the atmospheric pressure evaporator 161 to separate most of the methanol, which was treated with a methanol purification device 180 containing acid resins (DNW-I or D001) . Temperature of the purification device was maintained at room temperature to 80 . Liquid hourly space velocity (LHSV) was controlled at 0.35.0/h. The concentration of nitrogen-containing impurities in methanol after treatment was below 50 ppm. The methanol separated was reused together with fresh methanol in the transesterification reactor 150. The effluent from the bottomof the atmospheric pressure evaporator 161 comprised small amount of methanol, PG and transesterification catalyst. The effluent from the bottom of the atmospheric pressure evaporator 161 was treated with vacuum evaporator 162 to separate the transesterification catalyst, which was recycled. The effluent from the vacuum evaporator 162 comprised small amount of methanol and PG. The effluent from the vacuum evaporator 162 was treated with vacuum distillation tower 163 to separate methanol and PG. The methanol separated from the vacuum distillation tower 163 was treated with the methanol purification device 180 and reused in the transesterification reaction. The PG separated from the vacuum distillation tower 163 was used in the alcoholysis reactor 110. The effluent from the top of the transesterification reactor 150 was an azeotrope comprises methanol and DMC. The azeotrope was treated with the extraction tower 171 to separate methanol from the top of the tower and an effluent comprising DMC and extractant from the bottom of the tower. The methanol separated from the top of the extraction tower 171 was treated with the methanol purification device 180 and then reused together with fresh methanol in the transesterification reactor 150. The effluent from the bottom of the extraction tower 171 was treated with an extractant-regeneration tower 172 to separate the extractant and the DMC. The extractant separated was reused in the extraction tower 171. The yield of DMC was over 95. The heat at the top of the extraction tower 171 was collected and used in the transesterification reactor 150, thus minimizing the energy consumption. | |
With alkaline resin catalyst at 60 - 65℃; | 1 the Reaction distillation column has 28 pieces of plates (Section 2-7 for the distillation section, the first 8-22 block for the catalytic reaction section, the first 23-27 block for the distillation section). Among them, methanol is added from the 22nd plate, the feed flow rate is 18240 kg / h, and the propylene carbonate is added from the eighth plate, the feed flow rate is 7140 kg / h. Using nitrogen-containing alkaline resin catalyst, reaction temperature 60-65 ° C, operating pressure 0.1MPa, the conversion of propylene carbonate is 99.9%. | |
With calcium aluminium fluoride layered double hydroxide at 59.84℃; for 2h; | ||
With graphitic carbon nitride at 139.84℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
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With 2-methylimidazole; In N,N-dimethyl acetamide; at 154℃; for 4h; | A. Preparation of THPE PO (in DMAC solvent) A 1000 mL three neck flask equipped with a mechanical stirrer, condenser, thermocouple, and addition funnel was charged with THPE (50 g, 0.16 mol), propylene carbonate (66.2 g, 0.65 mol), 2-methylimidazole (1.3 g, 0.016 mol), and DMAC (200 mL). The solution was heated to 154° C. using a heating mantle and held for four hours. The brown solution was allowed to cool to 100° C. and 250 mL water was then added through the condenser to give a reddish solution. On cooling to room temperature, and oily layer formed at the bottom of the flask. The liquid layer was decanted off and the oil taken up in acetone (100 mL) and heated to reflux. To the solution was added 300 mL water. An oil layer again separated at the bottom of the flask. The liquid was decanted off and oil taken up in 400 mL CH2Cl2 and dried over MgSO4. Solvent was removed in vacuo to give 68.2 g (87percent) of the desired product as a thick, tacky oil. We discovered that the oil solidified on trituration with diethyl ether to give a white solid. 1H NMR (500 MHz, CDCl3) delta 1.35 (d, 9H), 2.18 (s, 3H), 2.37 (br s, 3H), 3.85 (m, 3H), 4.00 (m, 3H), 4.3 (m, 3H), 6.8 (m, 6H), 7.06 (m. 6H); 13C NMR (125 MHz, CDCl3) delta 18.7, 50.7, 66.3, 73.3, 113.8, 129.9, 142.2, 156.6. |
Yield | Reaction Conditions | Operation in experiment |
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In butyl carbitol formal; xylenes at 90 - 100℃; Inert atmosphere; | 7 Example 7; A 500 mL flask was purged with nitrogen and was charged with 3,3'-diaminodipropylamine (24.0 g, 0.183 mol), xylenes (40.0), and 1.80 g of a 14.4% (w/w) mixture of TBD in butyl carbitol formal that was heated to 100° C. in order to dissolve the TBD. To the stirred solution, propylene carbonate (19.00 g, 0.186 mol) was added and the reaction was allowed to exotherm. After the exotherm, the reaction was heated to 90° C. for 2 h. The reaction was allowed to cool to 70° C. and dipropylene glycol monobutyl ether (250.0 g) was added to the reaction vessel. The reflux condenser was replaced with a steam condenser and xylene filled Dean-Stark trap. The temperature was then held at 218° C. for 6 h. The temperature was then increased to 240° C. and held for 50 h. The yield as determined by HPLC was 90%. |
Yield | Reaction Conditions | Operation in experiment |
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69.2%; 12.5%; 13.2% | With 6,7,9,10,12,13,20,21-octahydrodibenzo[b,h][1,4,7,10,13,16]hexaoxacyclooctadecine; potassium chloride; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure; | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min. |
62.9%; 14.4%; 12.5% | With 6,7,9,10,12,13,20,21-octahydrodibenzo[b,h][1,4,7,10,13,16]hexaoxacyclooctadecine; potassium bromide; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure; | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min. |
44.1%; 6.7%; 5.8% | With potassium bromide; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure; | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min. |
41.7%; 29.8%; 23% | With 6,7,9,10,12,13,20,21-octahydrodibenzo[b,h][1,4,7,10,13,16]hexaoxacyclooctadecine; potassium chloride; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure; | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min. |
35.9%; 7.8%; 7.8% | With potassium chloride; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure; | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min. |
Yield | Reaction Conditions | Operation in experiment |
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54.8% | With lithium iodide; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure; | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min. |
Yield | Reaction Conditions | Operation in experiment |
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1: 91% 2: 90 %Chromat. | With [bis({2‐[bis(propan‐2‐yl)phosphanyl]ethyl})amine](bromo)(carbonyl)(hydride)iron(II); potassium <i>tert</i>-butylate; isopropyl alcohol In tetrahydrofuran at 140℃; for 6h; Inert atmosphere; Schlenk technique; Green chemistry; | |
1: 91% 2: 51 %Chromat. | With potassium <i>tert</i>-butylate; hydrogen; C16H18BrCoINO2 In dibutyl ether at 160℃; for 36h; | |
1: 82% 2: 75% | With [Mn(HN(C2H4PiPr2)2)(CO)2Br]; hydrogen; sodium t-butanolate In tetrahydrofuran at 120℃; for 26h; Schlenk technique; Glovebox; Autoclave; |
1: 99 %Chromat. 2: 99 %Chromat. | With [carbonylchlorohydrido{bis[2-(diphenylphosphinomethyl)ethyl]amino}ethylamino] ruthenium(II); potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran at 140℃; for 10h; Autoclave; | |
With hydrogen In tetrahydrofuran at 159.84℃; for 10h; | ||
1: > 99 %Chromat. 2: > 99 %Chromat. | With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium carbonate In isopropyl alcohol at 140℃; Glovebox; | |
1: 99 %Chromat. 2: 98 %Chromat. | With potassium phosphate; C62H63N5OPRu(1+)*Cl(1-); hydrogen In tetrahydrofuran at 140℃; for 24h; Glovebox; Autoclave; | |
With C21H35BrMnN2O2P; hydrogen; potassium hydride In toluene at 110℃; for 50h; Autoclave; | ||
1: 99 %Chromat. 2: 85 %Chromat. | With C23H21MnN2O3P(1+)*Br(1-); potassium <i>tert</i>-butylate; hydrogen In 1,4-dioxane at 140℃; for 16h; Autoclave; | |
1: 96 %Chromat. 2: 90 %Chromat. | With cobalt(II) tetrafluoroborate hexahydrate; hydrogen; 1,1,1-tris(di(3,5-dimethylphenyl)phosphinomethyl)ethane In 2,2,2-trifluoroethanol at 120℃; for 18h; Schlenk technique; Autoclave; | |
With potassium <i>tert</i>-butylate; hydrogen; C39H37N2OP2Ru(1+)*Cl(1-) In tetrahydrofuran at 140℃; for 3h; Glovebox; Autoclave; | 9-14 Example 14: Hydrogenation of cyclic carbonate catalyzed by ruthenium complex 1a In the glove box,To a 125 mL autoclave, add ruthenium complex 1a (7.5 mg, 0.01 mmol), potassium tert-butoxide (2.3 mg, 0.02 mmol), tetrahydrofuran (20 mL),Cyclic carbonate (20 mmol).After sealing the autoclave, remove it from the glove box,Fill with 50atm hydrogen. The reaction kettle was heated and stirred in a 140°C oil bath for a specific period of time. After cooling the reaction kettle in an ice water bath for 1.5 hours, the excess hydrogen was slowly released.With p-xylene as the internal standard, use gas chromatography (using the standard curve method, that is, with p-xylene as the internal standard, for cyclic carbonate,Methanol and diol are used as standard curves on the gas chromatography with the ratio of the peak area to the peak area of para-xylene. By measuring the ratio of the peak area in the reaction system, the cyclic carbonate contained in the reaction system mixture after the reaction is determined , The quality of methanol and glycol.The same gas chromatography method as in Example 9 was used to determine the conversion of cyclic carbonate and the yield of methanol and diol. The results are shown in Table 6. | |
With [carbonylchlorohydrido{bis[2-(diphenylphosphinomethyl)ethyl]amino}ethylamino] ruthenium(II); hydrogen In tetrahydrofuran at 140℃; for 16h; | ||
With hydrogen | 3 Example 3 CO2 Conversion to Methanol and Propylene Glycol One- and two-step processes for converting CO2 to methanol and propylene glycol (PG; also known as 1,2-propanediol, 1,2-PD) were evaluated. The reaction and catalyst are shown below. In the one-step process, propylene oxide (PO), a hydrogenation catalyst, and hydrogen were simultaneously added, and the propylene carbonate (PC) formed in step (a) immediately reacted with the catalyst and H2 in step (b) to form methanol and 1,2-PD. Two-step processes included (i) reaction with PO (step (a)) followed by addition of the hydrogenation catalyst and hydrogen and subsequent reaction to form methanol and 1,2-PD (step (b)), and (ii) reaction with PO in the presence of the hydrogenation catalyst to form PC (step (a)), followed by addition of hydrogen and reaction to form methanol and 1,2-PD (step (b)). |
Yield | Reaction Conditions | Operation in experiment |
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With pyridine at 31℃; | 1 Example 1 : HCI is oxidized to chlorine according to the procedure as described in US 20100303710 and subsequently purified as described therein. A chlorine enriched gas mixture (99.9 wt% chlorine, 0.09 wt% O2) from the just- described oxidation step is fed to a reactor, together with the CO-containing feed stream. The overall feed rates of these streams are 2.53 Nm3/hr and 2.4 Nm3/hr, respectively. The reaction is executed at a pressure of 4.3 bar and a temperature of 64°C, and a mixture consisting of 96.1 wt% phosgene, 3.8 wt% unreacted chlorine and other gases such as carbon dioxide, hydrogen chloride, and hydrogen is obtained. This mixture is fed to a reactor containing industrial grade propylene glycol (98 wt%, 2 wt% water), which is fed at a rate of 8.9 kg/hr, and a co-feed of pyridine, which is fed at a rate of 46 g/hr. The gas mixture and the liquid components are mixed intimately over a carbon catalyst ex Norit (Cabot Norit Activated Carbon Norit RB4C). Gaseous HCI is removed from the reactor in a continuous fashion, and is sent to the oxidation step after separation of the higher boiling compounds, which are returned to the reactor. After reaction at 31 °C and 1 .8 bar, the reaction mixture is fed to a separation section where it is separated via distillation into a carbonate-rich stream, consisting of 99.7 wt% propylene carbonate at a rate of 1 1 .4 kg/hr, a gaseous stream containing HCI and trace amounts of CO2, and at a rate of 0.4 kg/hr, a minor liquid stream containing mainly unreacted propylene glycol. The latter stream is recycled to the phosgenation reactor without further purification. Even though the propylene glycol contains 2 wt% of water, with the process according to the present invention, a yield of 99.7 wt% of propylene carbonate based on the theoretical maximum is obtained. Furthermore, due to the configuration of this process negligible amounts of phosgene are emitted. Finally, due to the closure of the chlorine cycle an environmentally friendly process is obtained |
Yield | Reaction Conditions | Operation in experiment |
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72.7% | With ZnCl2 supported on mesoporous graphitic carbon nitride In N,N-dimethyl-formamide at 140℃; for 6h; Autoclave; | |
63.54% | With C32H32N12Ni(2+)*2ClO4(1-)*2H2O; tetrabutylammomium bromide at 100℃; for 1.5h; Autoclave; | 2.4. general procedure for the reaction of epoxides and CO2 A 100 mL stainless-steel reactor was charged with purifiedpropylene oxide (PO) and catalyst. The air in the reactor wasreplaced by CO2 for 3 times, and the pressure in reactor wasadjusted to desired pressure by CO2. Then, the reactor was pressurizedwith carbon dioxide and heated to the desired temperatureby stirring. After reaction, the autoclave was cooled down to roomtemperature, and the CO2 pressure was released by opening theoutlet valve. The solid residue was separated from the reactionmixture by filtration. The product propylene carbonate (PC) wasobtained through distillation of the filtrate under reduced pressure.A qualitative analysis of the liquid products was performed on IRspectrum. For quantitative determination, the products wereanalyzed on an Agilent 6890 Plus GC with flame ionization detection. |
99 %Chromat. | With potassium iodide; L-Tryptophan at 120℃; for 1h; Autoclave; | 2.1 Cycloaddition of propylene oxide with CO2 All the cycloaddition reactions were conducted in a 25mL stainless-steel reactor equipped with a magnetic stirrer and self-acting temperature control system. In the typical procedure, desired amounts of catalyst (KI/l-tryptophan) and propylene oxide (PO) were added into the reactor. Then, CO2 was charged in the reactor and the pressure was adjusted to 2MPa at 120°C, and the stirrer was started. The reactor was maintained at 120°C for 1h, and the pressure was kept constant by means of a CO2 cylinder connected to the reactor during the reaction. After the reaction was completed, the autoclave was cooled to ambient temperature, and the excess CO2 was vented. The catalyst was separated from the reaction mixture by vacuum distillation, and the product yields were determined by GC and GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
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1: 46% 2: 31.2% | With sodium ethanolate; potassium iodide at 169.84℃; for 4h; | Catalytic activity test General procedure: In a typical catalytic evaluation, 45 mmol EO, 31.4 g ethanol and0.2 g total amount of catalyst were added into a stainless autoclavereactor with an inner volume of 150 mL. CO2 was introduced withan initial pressure of 3.0 MPa at room temperature, and the autoclavewas completely sealed. The reactor was heated and stirredconstantly at desired temperature (e.g. 423 K) during the reaction.The reaction was conducted in a batch operation mode. After thereaction, the reactor was cooled to room temperature and the residualgas was depressurized slowly passing through the trap withethanol as an absorbent. The compositions of the resulting mixturewere measured by GC-MS (Agilent 6890N/5975B). In order toquantitatively analyze the composition of the resulting mixture, theliquid products were analyzed by a gas chromatograph (Shimadzu)with a capillary column (Rtx-WAX 30 m×0.25 mm×0.25 m)equipped with a flame ionization detector (FID) and an automaticsampler using an external standard technique. The yield of productwas defined and calculated as follows: |
Yield | Reaction Conditions | Operation in experiment |
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67.2% | With 1-methyl-3-butylimidazolium N,N-dimethyl-3-amino-1-propylsulfonate; In acetonitrile; at 150℃; under 3750.38 - 7500.75 Torr; for 24.5h;Autoclave; Sealed tube; | The catalyst is 1-methyl-3-butylimidazolium hydroxideWeigh 2.5g of 1,2-propanediol and 10g of acetonitrile solvent (mass ratio of solvent to 1,2-propanediol is 4), and add 0.051g (3.29×10-4mol) of catalyst to the glass casing of 25mL autoclave. After the autoclave was sealed, it was slowly purged with a carbon dioxide gas stream for 5 min, then charged with 0.5 MPa of carbon dioxide, stirred at 150 C for 30 min until the temperature stabilized, and then the carbon dioxide pressure was adjusted to 1 MPa. After reacting for 24 hours, the reaction vessel was naturally cooled to room temperature, and carbon dioxide was slowly evolved to obtain propylene carbonate. After extracting with 10 mL of diethyl ether, add the internal standard, and take a small amount of sample for gas chromatography analysis.The internal standard yield of propylene carbonate was 35.4%.;The reaction conditions and preparation steps were the same as in Example 1, except that the mass of acetonitrile was 20 g (mass ratio of solvent to 1,2-propanediol was 8). After extracting with 10 mL of diethyl ether, an internal standard was added, and a small amount of sample was taken for gas chromatography analysis, and the internal standard yield of propylene carbonate was 38.1%.;The catalyst is 1-methyl-3-butylimidazolium N,N-dimethyl-3-amino-1-propane sulfonateThe reaction conditions and preparation steps were the same as in Example 2, except that the catalyst was 1-methyl-3-butylimidazolium N,N-dimethyl-3-amino-1-propanesulfonate (0.1 g, 3.29). ×10-4 mol). After extracting with 10 mL of diethyl ether, the internal standard was added, and a small amount of the sample was taken for gas chromatography analysis. The internal standard yield of propylene carbonate was 67.2%. |
99%Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene; 2-methyl-but-3-yn-2-ol; In N,N-dimethyl-formamide; at 120℃; under 22502.3 Torr; for 10h;Autoclave; | General procedure: The reactions were performed in a 50 ml autoclave with a Teflon vessel inside equipped with magnetic stirring under 3.0 MPa CO2. After introducing DBU (60.8 mg, 0.4 mmol), <strong>[57-55-6]propylene glycol</strong> (76.1 mg, 1 mmol), 2-methyl-3-butyn-2-ol (126.2 mg, 1.5 mmol), DMF (2 ml), the autoclave was sealed and filled with CO2 to keep thepressure of CO2 under 3.0 MPa. Then, the reaction mixture was stirred at 120 C for 10 h. When the reaction completed, the autoclave was cooled to ambient temperature and residual CO2 was carefully released. Subsequently, the mixture was flushed with DMF and analyzed by GC using biphenyl as an internal standard. |
With 2-Cyanopyridine; cerium(IV) oxide; at 140℃; under 60006 Torr; for 1h;Autoclave; | In examples 15 through 47, a carbonate ester was obtained from an alcohol and CO2 using 2-cyanopyridine under the conditions in which at least one of presence/absence of the solvent, the type of the solvent, the amount of the solvent, the reaction time, the type of the alcohol (substrate), the concentration of the alcohol (substrate), the type of the catalyst, and the amount of the catalyst was different from that in example 14. Specifically, the conditions different from those in example 14 were the type and the amount of the solvent in examples 15 through 18, 41 and 45 through 47 (regarding the solvent, ?-? indicates that no solvent was used), the reaction time in examples 18 through 21, 23 through 30, 33 through 39, 43 and 45 through 47, the value of the alcohol/2-cyanopyridine as the materials in examples 23 through 28, 35, 37, 42 and 45 through 47, the amount of the catalyst in examples 25 through 30, 35, 37 and 45 through 47, the type of the catalyst in examples 31 through 34, the temperature of the reaction solution in examples 37 through 47, the reaction pressure in examples 43 and 44, and the type, the amount and the like of the alcohol as the material in examples 35 through 47. (0166) Table 6 below shows the results of the examples of production of the carbonate ester. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | Stage #1: trimethylsulfoxonium iodide With sodium hydride In dimethyl sulfoxide at 25℃; for 0.0833333h; Inert atmosphere; Stage #2: acetaldehyde In tetrahydrofuran; dimethyl sulfoxide for 1h; Inert atmosphere; Stage #3: carbon dioxide In tetrahydrofuran; dimethyl sulfoxide at 40℃; for 6h; Inert atmosphere; | General Experimental Procedure for the Preparation ofCyclic Carbonates 4a-v General procedure: NaH (0.132 g, 3.3 mmol; previously washed with anhydrousPE to remove oil) was taken in an oven-dried three-neckedflask, followed by addition of anhydrous DMSO (10 mL)through a septum to it, and the whole slurry was stirred at 25°C under N2 atmosphere. Solid Me3SOI (0.726 g, 3.3 mmol)was added to the slurry with stirring over a period of 5 minvia a solid addition funnel until it becomes a homogeneoussolution. A solution of aldehyde 1a-v (3 mmol), dissolved inanhydrous THF (10 mL), was added dropwise to the reactionmixture. After 1 h, CO2 (1 atm) was then bubbled slowly viaa needle into the reaction mixture, (after ascertaining thataldehyde was completely converted into epoxide, monitoredby TLC) at 40 °C, for 6 h. Water (10 mL) was added toquench the reaction. It was then extracted with EtOAc (3 ×20 mL); the organic layer was washed with brine and driedover anhydrous Na2SO4 and the solvent concentrated,product purified by silica gel column chromatography (100-200 mesh) using PE and EtOAc (70:30) as eluent to affordpure cyclic carbonates 4a-v. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.8% | With zinc-magnesium mixed oxide at 169.84℃; for 0.5h; Green chemistry; | 2.2 Catalytic test. The reaction was performed in a 250 ml three-necked-flask, which was equipped with a magnetic stirrer, double condenser pipe along with gas-liquid separators, vacuum pump and temperature-controlled instrument. Typically, 30 g urea, 57 g PG and 0.6 g catalyst were added into the reactor, heated and kept at 443 K for 30 min at the pressure of 300 mm Hg. After reaction, the product was cooled to room temperature and the solid catalyst was separated from the liquid by centrifuge. The product was analyzed with a gas chromatography equipped with a DB210 (30 m × 0.32 mm) capillary column and a FID detector. The major components were PC and PG. Trace of dipropylene glycol (DPG), hydroxypropyl carbamate (HPC) and 4-methyl-2-azole alkane ketone (MOZD) was detected [14]. |
94.1% | With zinc(II) chloride at 160℃; for 3h; Ionic liquid; | 15 Example 15 Into a 100 mL three-necked flask equipped with a condensing device, 1.03 g of urea, 5 mL of propylene glycol and 0.19 g of zinc chloride, and 0.24 g of 1-hexadecyl-3-methylimidazolium chloride ionic liquid catalyst (zinc chloride and The molar ratio of the imidazole ionic liquid is 2:1; the molar ratio of ionic liquid to urea is 0.040:1), heated to 160 ° C by a collector type constant temperature heating stirrer, and the reaction pressure is controlled by a vacuum pump to be 15 KPa, and the reaction is 3.0 h. Thereafter, the heating was stopped, the temperature was cooled to room temperature, and the pressure in the reaction apparatus was returned to normal pressure; the Agilent gas chromatograph 6820 GC-TCD detector was used for quantitative analysis to obtain a propylene carbonate yield of 94.1%. |
94.1% | With 1-hexadecyl-3-methylimidazolium chloride; zinc(II) chloride In neat (no solvent) at 160℃; for 3h; Green chemistry; | 2.3. Typical procedure for the synthesis of EC from EG and urea General procedure: The urea alcoholysis reaction was operated in a 50 mL three-neckedflaskwith a reflux condenser, magnetic stirrer and an absorption device.A series of ILs (Scheme 2) were tested for comparisons. In a typical procedure,urea (1.8 g), EG (5 mL), C16mimCl (0.41 g) and ZnCl2 (0.33 g)were added into the three-necked flask. Then itwas heated to 160 °C reactiontemperature gradually and adjusted to the initial value under reducedpressure at the same time, because a great deal of ammonia couldbe produced in this reaction and itmust be released through an absorptiondevice from the reaction system. At the end of this reaction, themixtures were cooled at room temperature, and they were analyzedon a gas chromatograph equipped with 6820GC-TCD gas chromatographyof Agilent Technologies. The alike procedurewas also carried out forthe ureawith other diols. The tests of catalyst recyclingwere performedin a -100mL three-necked-flaskwith a scale-up experiment of 10 timesamount of urea, EG and catalyst. Since IL has high boiling points comparedwith organic compounds (EG and EC), IL and ZnCl2 could be separatedfrom products by distillation under vacuum and can be reusedfor the next run directly. |
76.3% | With metal porphyrin ion framework 1 at 160℃; for 3h; | 13 Example 1 General procedure: Into a 25mL three-necked flask equipped with a condensing device were added 5mmol urea,20mmol ethylene glycol and 190mg (2% mol urea) metal porphyrin ion framework 1 powder,Use a heat-collecting constant temperature heating stirrer to heat to 150°C,At the same time, use a vacuum pump to control the reaction pressure to 15kPa. After 3 hours of reaction,Stop heating and cool to room temperature,Return the pressure in the reaction device to normal pressure;The yield of ethylene carbonate was 67.8%. |
73.2% | With boiler ash containing potassium silicate (BA 900) at 150℃; for 10h; Inert atmosphere; | |
70% | With zinc(II) chloride In 1,2-dichloro-ethane at 84℃; for 24h; Inert atmosphere; | |
With zinc monoglycerolate In neat (no solvent) at 140℃; for 24h; Green chemistry; | ||
With ionic liquid catalyst at 50 - 200℃; for 0.1 - 6h; Large scale; | In a set of device used for production of propylene carbonate from 5,000tons urea, first transport the ionic liquid and propylene glycol into apre-reaction device (1), preheat. After attaining the temperature, introduceurea to pre-reaction device (1). The pre-reaction temperature is 50 -200 .The pre-reaction time is 0.1h-6h. After the pre-reaction liquid reaches therequired level, the pre-reacted feed stream, from the middle unit, isintroduced to the propylene carbonate reactive distillation column (2). Duringthe reactive distillation process, propylene glycol, propylene carbonate, andionic liquid catalyst (as heavier component) are transported from upper portionof the column to the bottom of the column. The resulting nitrogen is a lightcomponent. Separate it from the top of the column. The reactive distillationtemperature is 100-200C. Urea in tower bottoms is the upper part of thecatalyst separation device (3), are introduced to propylene carbonatepurification column (4). Propylene carbonate, as a heavier component, is movedfrom the upper portion of the column into the bottom of the column. When thepropylene carbonate content of the bottom column is more than 99.9%, removeproducts. Propylene glycol, the lighter component, is distilled off from theupper part of the column and recovered as a raw material. The operatingtemperature of the purification column is from 70 ° C -200 ° C. Catalyst can bereused 100 times and the catalytic effect is still very good. | |
With metal oxides alcoholysis catalyst at 130 - 170℃; | 1 The following is an example of producing DMC using the process illustrated in FIG. 2. As illustrated in FIG. 2, carbon dioxide and ammonia were fed into urea synthesis device 101 and dehydrated to produce melt urea. The melt urea so generated and PG were fed into an alcoholysis reactor 110 at molar ratio2: 1 together with an alcoholysis catalyst to produce PC and ammonia. The alcoholysis catalyst used was a solid complex catalyst comprising at least two metal oxides, wherein the metals were selected from the group consisting of copper, zinc, magnesium, aluminum, iron, zirconium, and titanium (produced by Yashentech Corporation) . The alcoholysis catalyst is present at around 0.31.0 (wt). The alcoholysis reactor 110 used was a continuous feed tank reactor. The range of the alcoholysis reactor temperature was from 130 to 170 . The pressure of the alcoholysis reactor 110 was within 2040kPa. Under conditions described above, PG and urea reacted in the presence of alcoholysis catalyst to generate PC and ammonia. The ammonia generated was treated via a purification device 120 to remove impurities. Purified ammonia was used to react with CO2 in the urea synthesis device 101 to produce urea, thus forming recycled use of ammonia. The effluent of the alcoholysis reaction 110 contained PC, PG and alcoholysis catalyst. The effluent was then treated with a catalyst-separating device 130 to separate the alcoholysis catalyst. The recovery rate of the alcoholysis catalyst is more than 99.9, and wet content of the alcoholysis catalyst was less than 50. The effluent of the alcoholysis reaction was further treated with a vacuum distillation tower 141 to separate the PC and PG. The PG separated was reused in the alcoholysis reaction in the alcoholysis reactor 110. The PC-containing effluent of the vacuum distillation tower 141 was treated with a vacuum distillation tower 142, and a vacuum distillation tower 143 to obtain PC. The PC obtained was fed to a transesterification reactor 150 to react with methanol in the presence of a transesterification catalyst. The transesterification reactor 150 was a catalytic distillation tower reactor. The molar ratio of methanol to PC in the transesterification reaction was around 10: 1 to around 25: 1. The transesterification catalyst was NaOCH3. The transesterification catalyst was present at around 0.3 1.2 (wt) . The reaction condition of the transesterification reactor 150 was as follows: atmospheric pressure temperature for the bottom of the tower was from 75 to 95 temperature at the top of the tower was from 65 to 70 . The effluent from the bottom of the transesterification reactor 150 contained methanol, PG and transesterification catalyst the effluent from the top of the tower was an azeotrope comprising methanol and DMC. The effluent from the bottom of the transesterification reactor 150 was treated with the atmospheric pressure evaporator 161 to separate most of the methanol, which was treated with a methanol purification device 180 containing acid resins (DNW-I or D001) . Temperature of the purification device was maintained at room temperature to 80 . Liquid hourly space velocity (LHSV) was controlled at 0.35.0/h. The concentration of nitrogen-containing impurities in methanol after treatment was below 50 ppm. The methanol separated was reused together with fresh methanol in the transesterification reactor 150. The effluent from the bottomof the atmospheric pressure evaporator 161 comprised small amount of methanol, PG and transesterification catalyst. The effluent from the bottom of the atmospheric pressure evaporator 161 was treated with vacuum evaporator 162 to separate the transesterification catalyst, which was recycled. The effluent from the vacuum evaporator 162 comprised small amount of methanol and PG. The effluent from the vacuum evaporator 162 was treated with vacuum distillation tower 163 to separate methanol and PG. The methanol separated from the vacuum distillation tower 163 was treated with the methanol purification device 180 and reused in the transesterification reaction. The PG separated from the vacuum distillation tower 163 was used in the alcoholysis reactor 110. The effluent from the top of the transesterification reactor 150 was an azeotrope comprises methanol and DMC. The azeotrope was treated with the extraction tower 171 to separate methanol from the top of the tower and an effluent comprising DMC and extractant from the bottom of the tower. The methanol separated from the top of the extraction tower 171 was treated with the methanol purification device 180 and then reused together with fresh methanol in the transesterification reactor 150. The effluent from the bottom of the extraction tower 171 was treated with an extractant-regeneration tower 172 to separate the extractant and the DMC. The extractant separated was reused in the extraction tower 171. The yield of DMC was over 95. The heat at the top of the extraction tower 171 was collected and used in the transesterification reactor 150, thus minimizing the energy consumption. | |
at 140℃; for 3h; | 1 First-stage alcoholysis: The urea, propylene glycol and the first catalyst were fed in a molar ratio of 1: 2: 0.1 to a reactor equipped with a heated stirring and vacuum system at a temperature of 140 °C, Vacuum degree of 0.01~0.03 MPa under the conditions of reaction 3h, the formation of propylene carbonate and ammonia, Cooling and filtering the filtrate; wherein the ammonia gas is absorbed by a special device so as to avoid polluting the air; The first catalyst is a complex of zinc oxide, magnesium oxide and lanthanum oxide in a mass ratio of 3:2:0.5 |
Yield | Reaction Conditions | Operation in experiment |
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42% | With Amberlyst A 35 at 140℃; for 2h; | 14 Synthesis of Propylene Glycol Pentyl Ether by Acid Catalysis from Glycerol Carbonate EXAMPLE 14 Synthesis of Propylene Glycol Pentyl Ether by Acid Catalysis from Glycerol Carbonate In a 50-mL three-necked flask, provided with a coolant and a nitrogen inlet, 3.52 g (40 mmol) of commercial pentan-1-ol and 118 mg of Amberlyst A 35 solid acid are introduced at room temperature. The reaction medium is then brought to 140° C. and 118 mg (10 mmol) of propylene carbonate are added over a period of one hour. The heating at 140° C. is then extended for 1 h after the end of the addition. Then, the reaction medium is brought to room temperature. Then, 20 mL of CH2Cl2, as well as 5 mL of H2O are added. The organic phase is then decanted. The aqueous phase is extracted by 2*25 mL of CH2Cl2. The organic phases are combined and the CH2Cl2 is evaporated under reduced pressure. The crude reaction product is finally purified by flash silica column chromatography (Eluent (AcOEt/cyclohexane: 1/4 to 1/1)) to give propylene glycol 1-O-pentyl ether with an isolated yield of 42%. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: tert-butyl 3-hydroxyazetidine-1-carboxylate With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: 1,2-propylene cyclic carbonate In N,N-dimethyl-formamide at 120℃; | 22.1 step 1: To a solution of tert-butyl 3-hydroxyazetidine (2.5 g, 14.5 mmol) in DMF (100 mL) was added NaH (1.45 g, 36.3 mmol) at 0° C. and stirred for 30 min. After addition of 4-methyl-1,3-dioxolane-2-one (3 g, 29 mmol) the reaction was stirred at 120° C. overnight. The reaction mixture was cooled to RT and quenched by adding a saturated aqueous NH4HCO3 solution (5 mL). The mixture was concentrated under reduced pressure to afford tert-butyl 3-(2-hydroxypropoxy)azetidine-1-carboxylate (4 g) as yellow solid, which was used in the next step without further purification. LCMS (ESI): m/z=232.1 [M+1]+ |
Yield | Reaction Conditions | Operation in experiment |
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40% | With Amberlyst A 35 at 140℃; for 2h; | 15 Synthesis of Propylene Glycol Heptyl Ether by Acid Catalysis from Glycerol Carbonate EXAMPLE 15 Synthesis of Propylene Glycol Heptyl Ether by Acid Catalysis from Glycerol Carbonate In a 50-mL three-necked flask, provided with a coolant and a nitrogen inlet, 4.65 g (40 mmol) of commercial heptan-1-ol and 118 mg of Amberlyst A 35 solid acid are introduced at room temperature. The reaction medium is then brought to 140° C. and 118 mg (10 mmol) of propylene carbonate are added over a period of one hour. The heating at 140° C. is then extended for 1 h after the end of the addition. Then, the reaction medium is brought to room temperature. Then, 20 mL of CH2Cl2, as well as 5 mL of H2O are added. The organic phase is then decanted. The aqueous phase is extracted by 2*25 mL of CH2Cl2. The organic phases are combined and the CH2Cl2 is evaporated under reduced pressure. The crude reaction product is finally purified by flash silica column chromatography (Eluent (AcOEt/cyclohexane: 1/4 to 1/1)) to give propylene glycol heptyl ether with an isolated yield of 40%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.7 %Chromat. | With carbon dioxide; potassium iodide at 120℃; for 6h; Autoclave; | General procedure for the one-pot synthesis of DMC General procedure: General procedure for the one-pot synthesis of DMC The one-pot synthesis of DMC was carried out in a stainless steel autoclave reactor with a volume of 75 ml. A typical procedure was as follows: epoxide (14.3 mmol), methanol (214.5 mmol, 8.7 mL), Na2CO3 (5.0 mol%) and biphenyl (80 mg, an internal standard for GC analysis) were charged in the autoclave at room temperature. Then CO2 was introduced into the reactor, which was heated to 120 °C for 6 h. After cooling, the reaction mixture was analyzed by gas chromatograph. |
Yield | Reaction Conditions | Operation in experiment |
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52.4%; 5.7% | With lithium bromide; at 130℃; under 15001.5 Torr; for 8h;Autoclave; High pressure; | General procedure: The one-step synthesis of DMC from carbon dioxide, epoxides and methanol was carried out in a sealed Teflon-lined stainless steel high pressure autoclave with inner volume of 50mL provided with a magnetic stirrer and an electric heater. Typical conditions and procedures are described as follows: a certain amount of methanol, propylene oxide (PO), catalyst and cocatalyst were added into the above autoclave. Alkali halides were used as catalysts, several typical crown ethers (i.e., [2,4],-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) were used as cocatalysts, and polyethylene glycol (MW=4000, abbreviated as PEG4000) was used as comparison for the crown ether. Then CO2 (gas, > 99.99%) was injected up to a certain pressure at room temperature. The autoclave was heated to a certain temperature and the mixture was stirred at that temperature for several hours. After the reaction, the autoclave was cooled to about 10C with ice-water mixture and then depressurized. The liquid reaction mixture was analyzed by gas chromatograph (GC 2060) equipped with a capillary column (HP-INNOWAX, 30m×0.32mm×0.25mum) and flame ionization detector (FID) using n-butyl alcohol as an internal standard, and further identified by gas chromatography-mass spectrometry (Agilent 7890-5975C) by comparing retention times and fragmentation patterns with authentic samples. The temperature of the GC column was set at 60C for 3min and then was programmed to rise to 80C at the rate of 5Cmin-1, and further reached 220C at the rate of 30Cmin-1 and remained at that temperature for 3min. |
Yield | Reaction Conditions | Operation in experiment |
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91% | With IL(OAc-)-MIL-101-NH2 In neat (no solvent) at 140℃; for 9h; | |
90% | With C19H31KNO5(1+)*2C2H3O2(1-)*H(1+) at 130℃; for 12h; | |
83% | With triethylamine; adenine In neat (no solvent) at 120℃; for 18h; regioselective reaction; | General procedure for the synthesis of oxazolidinones General procedure: An 8 mL vial was charged with adenine (0.05 mmol, 6.7 mg), Et3N (0.5 mmol, 69 μL), aryl amine (1 mmol) and cyclic carbonate (6 mmol). The mixture was heated at 110 °C for 18 h, after which time 5 mL of water was added. The organic layer was extracted with dichloromethane (3 × 5 mL). The combined organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate = 5:1 as eluent). |
Yield | Reaction Conditions | Operation in experiment |
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85% | Stage #1: propene With oxygen; isobutyraldehyde In acetonitrile at 100℃; for 6h; High pressure; Stage #2: carbon dioxide In acetonitrile at 100℃; for 4h; High pressure; | |
49% | Stage #1: propene With piperidine; norbornene; manganese(II,III) oxide; 3-chloro-benzenecarboperoxoic acid In N,N-dimethyl-formamide at 90℃; for 2h; Stage #2: carbon dioxide In N,N-dimethyl-formamide at 20 - 130℃; for 6h; | 6 Weigh 1.0 mol of propylene and 1.4 mol of m-chloroperoxybenzoic acid.Nano-manganese tetraoxide 0.005 moles (as shown in Figure 2Show), 0.005 mol of iron acetylacetonate, 0.1 mol of norbornene, 1.1 mol of piperidine,1 liter of propylene carbonate, added to a 5 liter reactor equipped with a condensing reflux unit,Under stirring, slowly raise the temperature to about 90 ° C for 2 hours, and cool to room temperature;The dry carbon dioxide gas is introduced into the system from the conduit port to raise the pressure to 6 atm.The temperature was raised to 130 ° C for 6 hours. After cooling to room temperature, unreacted carbon dioxide was slowly evolved and worked up to obtain a product. The product was purified by distillation under reduced pressure, and the yield based on propylene was 49%. |
With oxygen In 1,4-dioxane at 150℃; for 5h; Autoclave; | 6 (Catalytic Oxidation of Propylene by CO2 Using Fe modified 2D and 3-D Carbon Nitride Materials of the Present Invention) The catalytic test was carried out in 66 ml autoclave as follows: propylene (23 mmol), catalyst (0.1 g, 5 wt.% Fe-KIT6-tetrazole and 5 wt.% Fe-SBA15-tetrazole), and 1,4-dioxane (3.0 ml) were added in the autoclave and the reaction was performed at the following conditions: reaction temperature (150 °C), CO2 pressure (3.5 MPa), and reaction time (5 h). The Fe-KIT6-tetrazole and 5 wt.% Fe-SBA15-tetrazole were prepared using the methods of Examples 1-3. The amount of O2 present in the autoclave was estimated to be about 1.5 mmol. After the reaction was over, the autoclave was cooled in cold water and the CO2 pressure released. Then, the reactor was opened, biphenyl was added as an external standard to the reaction product, the sample collected, centrifuged at 4000 rpm, and an aliquot of the sample injected into a gas chromatograph fitted with a flame ionization detector (GC-FID Agilent model 6890). Chromatography was performed on a capillary column DB-5ms from JW Scientific, Agilent Technologies, USA (30 m x 0.25 mm internal diameter coated with 0.25- μπι film thickness). Helium was used as the carrier gas at 2.5 mL/min, and the FID detector temperature was kept at 250 °C. Split injection (100: 1) with a sample volume of 1 μ. was applied. The oven temperature was increased from 45 to 170 °C at a gradient of 8 °C/min and finally to 250 °C, and held at this temperature for 5 min. Quantification of propylene carbonate was done by injecting known concentration of PC and biphenyl mixture. Analyses were also done in GC fitted with a mass selective detector (MSD) (Hewlett-Packard 5890 Series II, Agilent Technologies, USA) using a 30 m high resolution capillary column DB-5 (i.d. 0.25 mm, 0.25 μπι film) (JW Scientific, Agilent Technologies, USA) and followed the same temperature programming as GC-FID. The products were identified with MS library associated with the GCMS. Table 3 lists the yield and selectivity of propylene carbonate, which were calculated using the equations (i) to (ii) for styrene oxide substituting propylene carbonate for styrene oxide. In the reaction, the yield of the reaction is around 5 to 10% with a very high selectivity. It should be noted, that propylene carbonate is not made through CO2 addition to propylene oxide followed by cyclization as shown in the reaction scheme. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90 %Spectr. | Stage #1: propylene glycol; carbon dioxide With 1,8-diazabicyclo[5.4.0]undec-7-ene In 1,2-dichloro-ethane at 25℃; Stage #2: 1-bromo-butane In 1,2-dichloro-ethane at 25℃; for 24h; | General procedure for the synthesis of cyclic carbonates 2 General procedure: Compound 1 (2.5 mmol) and DBU (20 mmol) in DCE (1mL) were placed in a 50-mL two-necked flask and CO2 gas was flowed with stirring at 25 °C until the solution was changed to a white suspension. After addition of 1-bromobutane (24 mmol), the flask was capped with a rubber septum and equipped with a CO2 balloon. The mixture was stirred at 25 °C for 24 h and then passed through a short pad of silica gel with CH2Cl2 as eluent to remove the DBU salts. The eluent was concentrated under reduced pressure and the yield of the product was determined by 1H NMR using an internal standard. The product 2 was separated by column chromatography on silica gel using hexane and/or CH2Cl2 as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide Inert atmosphere; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With titanium silicalite molecular sieve TS-1 In acetone at 200℃; for 3h; | 19 Example 19 The epoxy propane, methanol, CO2, solvent acetone and the catalyst of the step (1) preparation of the titanium silicon molecular sieves TS-1 into a high-pressure reactor, the uniformly mixing 60 °C stirring for 3 hours. Wherein epoxy propane, methanol and CO2molar ratio of 1:4:25, the weight ratio of the solvent with the catalyst 50:1, epoxy propane and of the weight of the catalyst ratio of 20:1, high-pressure reaction kettle as to control the pressure of 0.6 MPa. Furthermore, the obtained mixture is filtered, the gas phase chromatography to measure the composition of the liquid phase mixture, and calculating the epoxy propane conversion and selectivity of propylene glycol monomethyl ether and propylene carbonate, results in table 2 are listed in the.; With the embodiment of the 15 the same method for preparing propylene glycol monomethyl ether and propylene carbonate, is different, step (2) in, temperature is 200 °C, results in table 2 are listed in the. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.5% | With octyltrimethylammonium bromide; toluene-4-sulfonic acid In toluene for 20h; Reflux; | 9 Example 3 18.248 g (0.1 mol) of 1-p-tolyl-2-chloro-1-propanone,20.407 g (0.2 mol) of propylene carbonate,1.726 g (0.01 mol) of anhydrous p-toluenesulfonic acid,0.371 g (0.001 mol) of tetrabutylammonium iodide and 150 ml of anhydrous toluene,Was placed in a reaction flask equipped with a water separator,The reaction mixture was refluxed for 20 h and cooled to room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.6% | With tetra-(n-butyl)ammonium iodide; toluene-4-sulfonic acid In toluene for 25h; Reflux; | 11 Example 11 The 22.708g (0.1mol) of 1-p-tolyl-2-bromo-1-propanone, 20.407g (0.2mol) propylene carbonate, 3.45g (0.02mol) of anhydrous p-toluenesulfonic acid, 0.075g ( 0.0002 mol) and tetrabutylammonium iodide in 120ml of anhydrous toluene, placed in a reaction flask equipped with a water separator and stirred under reflux for dehydration 25H, cooled to room temperature, HPLC analysis ketal yield 92.6% (1 in - calculation of toluene-2-bromo-1-propanone). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With potassium carbonate In methanol at 119.84℃; for 2h; Autoclave; Industrial scale; | 6.b in the original high-pressure reactor in the reaction liquid, by adding methanol 740mmol, potassium carbonate 4mmol, closed reactor, heating high-pressure reaction kettle until 393K, reaction 2h, the high-pressure autoclave after the reaction cooling to normal temperature, open the reaction kettle after decompression to atmosphere, gas chromatographic analysis of the reaction liquid, dimethyl carbonate to yield and the selectivity of 88% and 98%, the propylene glycol selectivity of 96%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.5% | In dichloromethane at 50℃; for 6h; | 2 Synthesis of carbamate-containing monomers: Necked flask equipped with a stirrer, a thermometer and a condenser was charged with 20.42 g of 20.42 g of methylene chloride in propylene carbonate and stirred for dissolution. Then, 14.2 g of pyrrolidine was weighed into the flask, and the dropping time was controlled at 0.3 h at 50 ° CUnder the reaction 6h. After completion of the reaction, the solvent was removed by extraction to give 35.38 g of product, and the yield was 93.5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.6% | In ethanol at 45℃; for 3h; | 4 Synthesis of Carbamate - containing Monomers To a four-necked flask equipped with a stirrer, a thermometer and a condenser, 51.05 g of propylene carbonate and 80 g of ethanol were added and dissolved with stirring. Then, 52.27 g of morpholine was weighed and added to the flask. The addition time was controlled at lh and reacted at 45 ° C for 3 h. After completion of the reaction, the solvent was removed by solvent displacement and combined with distillation under reduced pressure to obtain 96.71 g of the product. The yield of the product was 93.6%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62 %Chromat. | With potassium hydroxide In water at 115℃; for 24h; Inert atmosphere; | 13 Example 13 Novel nitrogen heterocyclic carbene metal complex assembly supported catalyst 4c for catalyzed oxidative dehydrogenation of propylene glycol carbonate Efficient preparation of lactic acid: (0.0045 mmol) of propylene carbonate (15 mmol), potassium hydroxide (16.5 mmol), and potassium hydroxide (16.5 mmol) were charged into a centrifuge tube in which a gas storage device was connected in succession under nitrogen atmosphere. Water (0.3 mL), heated to 115 ° C for 24 hours, the reaction process will be released hydrogen. After the reaction, the reaction solution was cooled to about 80 DEG C. A small amount of water was added to dilute the reaction solution and the gas storage device was removed. The temperature was lowered to room temperature, and the supernatant was decanted by centrifugation after low-speed centrifugation. The supported catalyst was repeatedly washed with distilled water and recovered. The aqueous solution was combined, and sodium acetate trihydrate was added as an internal standard after concentration. The yield of lactic acid was 62% by NMR, and the yield was further confirmed according to the amount of evolved hydrogen. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42.4% | With potassium carbonate In N,N-dimethyl acetamide at 150℃; for 10h; | 4 Into a 50 ml four-necked flask was charged 1.0 eq. Of the intermediate 1 obtained in Example 1-1.And 14.3 eq. Of dimethylacetamide..Propylene carbonate 1.1 eq.And potassium carbonate 0.02 eq.And the mixture was stirred at 150 ° C. for 10 hours.After cooling to room temperature, it was extracted with ethyl acetate and washed twice with ion exchanged water.The solvent was distilled off, and the crude product was purified by silica column chromatography (n-hexane: ethyl acetate = 1: 1) and dried to give Compound No. 1.42 (yield 42.4%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 160℃; for 3h; | 2 First-stage alcoholysis: The urea, pentaerythritol and the first catalyst were fed in a 1: 3: 0.3 molar ratio in a reactor equipped with a heated stirring and vacuum system at a temperature of 160 ° C and a degree of vacuum of 0.01 to 0.03 MPa under the conditions of reaction 3h, the formation of propylene carbonate and ammonia, after cooling filter filtrate; Wherein the first catalyst is a complex of zinc oxide, magnesium oxide and lanthanum oxide in a mass ratio of 5: 3: 1, wherein the first catalyst is a composite of zinc oxide, magnesium oxide and lanthanum oxide in a mass ratio of 5: 3: 1, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 95% 2: 67 %Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction; | 4-Methyl-1,3-dioxolan-2-one (5a); Typical Procedure (Table 2) General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and α-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 µm) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. 4-Methyl-1,3-dioxolan-2-one (5a) Colorless liquid; yield: 98 mg (95%). 1H NMR (400 MHz, CDCl3): δ = 4.84-4.92 (m, 1 H), 4.58 (t, J = 8.4 Hz, 1 H), 4.04 (t, J = 8.4 Hz, 1 H), 1.49 (d, J = 6.0 Hz, 3 H). 13C{1H} NMR (100.6 MHz, CDCl3): δ = 155.1, 73.7, 70.7, 19.4. |
1: 94 %Spectr. 2: 98 %Spectr. | With silver(l) oxide; N,N,N',N'-tetramethylguanidine In acetonitrile at 80℃; for 12h; Autoclave; | |
1: 98 %Spectr. 2: 92 %Spectr. | Stage #1: carbon dioxide; 2-methyl-but-3-yn-2-ol With C15H18N2O2 In acetonitrile at 25℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: propylene glycol With 1-methyl-2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine In acetonitrile at 80℃; for 24h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 95.3% 2: 97.6% | With potassium iodide at 160℃; for 10h; | 11 Example 11 Example 11In a 1:1 mixture of PO and piperazine-carbamate in a molar ratio of 1:1, 50 mL of a hydrothermal reaction crystallization vessel was added, and 1.0% mol of KI (ie, the mole percent of the total system) was added to the reaction vessel. The magnetic stirrer was used to control the temperature of 160 °C and the reaction time was 10 h. After the reaction, the mixture was naturally cooled to room temperature.PC yield 95.3%, piperazine yield 97.6% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 90.2% 2: 96.3% | With potassium fluoride at 100℃; for 0.5h; | 2 Example 2 According to PO and ethylenediamine - carbamate molar ratio of 6: 1 mixed into 50ml hydrothermal reaction crystallization kettle, add the reminderThe agent KF 0.5% mol (ie, the mole percent of the total system) is controlled by a thermostatically heated magnetic stirrer.The temperature was 100 °C, the reaction time was 0.5 h, and the reaction was naturally cooled to room temperature after the reaction.The PC yield was 90.2% and the ethylenediamine yield was 96.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With triethylamine; adenine In neat (no solvent) at 120℃; for 18h; regioselective reaction; | General procedure for the synthesis of oxazolidinones General procedure: An 8 mL vial was charged with adenine (0.05 mmol, 6.7 mg), Et3N (0.5 mmol, 69 μL), aryl amine (1 mmol) and cyclic carbonate (6 mmol). The mixture was heated at 110 °C for 18 h, after which time 5 mL of water was added. The organic layer was extracted with dichloromethane (3 × 5 mL). The combined organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate = 5:1 as eluent). |
85% | With IL(OAc-)-MIL-101-NH2 In neat (no solvent) at 140℃; for 9h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With triethylamine; adenine In neat (no solvent) at 120℃; for 18h; regioselective reaction; | General procedure for the synthesis of oxazolidinones General procedure: An 8 mL vial was charged with adenine (0.05 mmol, 6.7 mg), Et3N (0.5 mmol, 69 μL), aryl amine (1 mmol) and cyclic carbonate (6 mmol). The mixture was heated at 110 °C for 18 h, after which time 5 mL of water was added. The organic layer was extracted with dichloromethane (3 × 5 mL). The combined organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate = 5:1 as eluent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.7% | With 1-butyl-3-methyl-1H-imidazol-3-ium bromide; anhydrous zinc chloride at 100℃; for 8h; Autoclave; Sealed tube; | 18 Example 1 General procedure: In an 80mL stainless steel autoclave, add 500 mg of 1-butyl-3-methylimidazolium bromide (n=4 in the structural formula), 1.5 mmol of styrene oxide, and 30 mg of ZnCl2 auxiliary (the amount of auxiliary is epoxy compound) 15% of the molar weight), sealed the reaction kettle, filled with flue gas to 2.0MPa, and then controlled the temperature by a temperature controller to slowly rise to 100°C, and reacted for 6.0h. Cool to room temperature, open the exhaust valve and slowly release excess flue gas, open the reaction kettle, add biphenyl as an internal standard, the obtained product is analyzed by gas chromatograph, and the conversion rate of the obtained styrene carbonate is 98.7%, and the selectivity is 98.4 %. |
95.7% | With 1-carboxypropyl-imidazolium bromide at 120℃; for 2h; | 23 Trial 23: This test differs from the test ten in that the molar ratio of 1-carboxypropylimidazolium hydrobromide ionic liquid to propylene oxide is 1:100. The other steps and parameters were the same as in Test 10, and the obtained propylene carbonate yield was 95.70%.A method for catalytically synthesizing a cyclic carbonate by protonated carboxyimidazole ionic liquid is carried out according to the following steps:The protonated alkylpyrazole ionic liquid 1-carboxypropylimidazolium hydrobromide was added to a 100 mL autoclave, followed by 7 mL of epoxy compound propylene oxide, the 1-carboxypropylimidazolium hydrobromide salt. The molar ratio to propylene oxide is 1:200, the high pressure reactor is sealed, and the pressure in the high pressure reactor is 1.5 MPa, the temperature is raised to 120 ° C, and the reaction is carried out for 2 h. After the end of the reaction, the autoclave was cooled to room temperature, excess CO 2 was slowly evolved, and the product was distilled under reduced pressure to remove unreacted propylene oxide to obtain propylene carbonate in a yield of 92.41%. |
95% | at 25℃; for 24h; Inert atmosphere; Schlenk technique; | 6 General procedure: The specific experimental process and the detection method are as 2, and epichlorohydrin is changed into different substituents and other epoxides, and ring addition reaction with carbon dioxide respectively, and the results are shown in Table 1.Table 1 TBPB/3 - AP catalyses the addition reaction results of different epoxides with carbon dioxide rings.The catalyst TBPB PB PB PB PB of Example 1 and reactant epichlorohydrin 100 ml were added in this order, and the Munitz-connected CO was added.2Schlenlenk (Schlenk) reaction flask for balloons, wherein epichlorohydrin 10 mmol, TBPB-NHS 0.8 mmol, the catalyst accounts for epichlorohydrin mole content as 8 µM % , the internal remaining air is removed under reduced pressure; and the reaction bottle and CO are removed.2To the balloon, unitz , unitunitunitin 25 °C at the reaction temperature 0.1 mpa CO.2At the end of the reaction, the product 24 hours is subjected to quantitative analysis by gas chromatography, and the corresponding product corresponds to the units , and is of a 96% selected unitz-99% type. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83.1% | With tetrabutylammomium bromide; potassium carbonate at 110℃; for 2h; | 3 Example 3 Into a 100 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer,The compound (9,9-bis (2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran-5-yl) fluorene) obtained in Example 1 and represented by the above formula (7) 00 g (0.020 mol),30.00 g (0.294 mol) of propylene carbonate,0.66 g (0.002 mol) of tetrabutylammonium bromide,0.28 g (0.002 mol) of potassium carbonate was charged, and the temperature was raised to 110 ° C.When the mixture was stirred at the same temperature for 2 hours,As a result of analyzing the reaction solution by HPLC,The residual amount of the compound represented by the above formula (7) was 1.0% or less.The obtained reaction solution was cooled to 60 ° C., methanol and water were added, and the mixture was allowed to cool to room temperature. The precipitated crystals were filtered and dried to give the following formula (9)(Yield based on the compound represented by the above formula (7): 83.1%) as a greenish white crystal of the compound represented by the formula (7). The HPLC purity of this greenish white crystal was 82.6%.The measurement results of 1 H-NMR and 13 C-NMR of the obtained compound represented by the formula (9) are shown below |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With 3-methyl-2-butynyltetramethylenesulfonium hexafluoroantimonate at 90℃; for 0.333333h; | 9 Under nitrogen atmosphere, into a sufficiently dried Schlenk tube, 1.7 g of 1, 6-anhydro-ß-D-mannopyranose and 3.5 ml of dry propylene carbonate were charged. Then, the Schlenk tube was placed in an oil bath, and the oil bath was heated to 90 °C so as to thoroughly dissolve 1, 6-anhydro-ß-D-mannopyranose. Subsequently, 66 % by mass (11. 4 J. l) of 3-methyl-2-butynyltetramethylenesulfonium hexafluoroantimonate was added to allow polymerization to begin. After 20 minutes' reaction, the polymerization solution was poured into methanol to stop the polymerization reaction. After removing the solvent, reprecipitationwasrepeatedwithwaterandacetone. Theresultant solution was further dialyzed for purification and freeze-dried to obtain 1. 11 g of multi-branched polysaccharide C in white powder. The yieldwas 64 %. The multi-branchedpolysaccharide C was subj ected to 1H-NHR and 13 C-NMR analyses to confirm the structure. Moreover, the weight average molecular weight of the multi-branched polysaccharide C was 80,000 (light scattering method), and the branching degree was 0.43. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With 2-butynyltetramethylene sulfonium hexafluoroantimonate at 100℃; for 0.5h; | 1 Under nitrogen atmosphere, into a sufficiently dried Schlenk tube, 13.0 g of 1, 6-anhydro-ß-D-glucopyranose (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 12.5 ml of dry propylene carbonate (manufactured by Sigma-Aldrich Co. ) and 66 mass % of 2-butynyltetramethylene sulfonium hexafluoroantimonate (65.8 Ll) (manufactured by ASAHI DENKA CO. , LTD. ) were charged. Then, the Schlenk tube was placed in an oil bath, and the oil bath was heated to 100 °C so as to thoroughly dissolve 1, 6-anhydro-ß-glucopyranose. Subsequently, the oil bath was furtherheatedto 130 °Cwhile stirring, so as to allowpolymerization to begin. After 30 minutes'reaction, the polymerization solution was added into methanol to stop the polymerization reaction. After removing the solvent, reprecipitation was repeated with water and methanol. The resultant solution was further dialyzed for purification and freeze-dried to obtain 5.3 g of multi-branched polysaccharide A in white powder. The yield was 41 %. The multi-branchedpolysaccharideAwassubjectedto1H-NHRandl 3 C-NMR analyses to confirm the structure. Moreover, the weight average molecular weight of the multi-branched polysaccharide Awas 20, 000 (light scattering method), and the branching degree was 0.38. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With RuCl2[(Ph2PCH2CH2)2NH](t-Bu-NC); potassium <i>tert</i>-butylate; deuterium at 120℃; for 12h; | 42 Example 42. Deuteration of propylene carbonate using RuCl2[(Ph2PCH2CH2)2NH](t-Bu-NC) as catalyst The catalyst (30 mg) is added to a mixture of propylene carbonate (3.0 g) and KO'Bu (10 mg) in a 100 ml Parr pressure reactor. The mixture was degassed with deuterium gas and the pressure was set to 20 atm. The mixture was stirred for 12 hours at 120 °C. It was then cooled to room temperature. The NMR spectra of the reaction mixture showed 100% conversion of the ethylene carbonate to propylene glycol and deuterated methanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 91% 2: 67% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction; | 4-Methyl-1,3-dioxolan-2-one (5a); Typical Procedure (Table 2) General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and α-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 µm) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 87% 2: 59% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction; | 4-Methyl-1,3-dioxolan-2-one (5a); Typical Procedure (Table 2) General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and α-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 µm) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 69 %Chromat. 2: 71 %Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; | |
1: 76 %Chromat. 2: 80 %Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 120℃; for 10h; Autoclave; | General procedure for the reaction of vicinal diols, propargylic alcohols and CO2 General procedure: The reactions were performed in a 50 ml autoclave with a Teflon vessel inside equipped with magnetic stirring under 3.0 MPa CO2. After introducing DBU (60.8 mg, 0.4 mmol), propylene glycol (76.1 mg, 1 mmol), 2-methyl-3-butyn-2-ol (126.2 mg, 1.5 mmol), DMF (2 ml), the autoclave was sealed and filled with CO2 to keep thepressure of CO2 under 3.0 MPa. Then, the reaction mixture was stirred at 120 °C for 10 h. When the reaction completed, the autoclave was cooled to ambient temperature and residual CO2 was carefully released. Subsequently, the mixture was flushed with DMF and analyzed by GC using biphenyl as an internal standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 92% 2: 62% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction; | 4-Methyl-1,3-dioxolan-2-one (5a); Typical Procedure (Table 2) General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and α-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 µm) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With manganese(II) triflate bis-acetonitrile solvate; potassium <i>tert</i>-butylate In benzene-d6 at 20℃; for 3h; Inert atmosphere; Glovebox; | |
53% | With boric acid In 2-methyltetrahydrofuran at 200℃; for 4h; Microwave irradiation; | |
97 %Spectr. | With tris(bis(trimethylsilyl)amido)lanthanum(III) at 20℃; for 6h; Inert atmosphere; | 5 Example 5: La [N (SiMe3) 2] 3 catalyzes the synthesis of borate from propylene carbonate and pinacol borane Under a nitrogen atmosphere,Add the catalyst La [N (SiMe3) 2] 3 (3.1mg, 0.005mmol) to the reaction bottle after dehydration and deoxidation treatment,Add with a pipettePropylene carbonate(84.8 μL, 1 mmol), and then add pinacol borane (478.8 μL, 3.3 mmol) with a pipette.After 6h reaction at room temperature, contact the air to stop the reaction,Pipette a drop into the NMR tube,Add CDCl3 to make a solution.The calculated 1H spectrum yield was 97%.NMR data of the product. |
99 %Spectr. | With C42H50Mg2N4 for 6h; | 2 Example 2 The β-diimine monovalent magnesium compound catalyzes the reaction of propylene carbonate with pinacol borane as follows:In a glove box, a reaction flask was added successively a monovalent β-carbodiimide magnesium compound 1mol%, 0.4 mmol propylene carbonate, The pinacol borane 1.6 mmol was then removed from the glove box and stirred for 6 h. The yield was 99% by NMR |
92 %Spectr. | With dibutylmagnesium In n-heptane; (2)H8-toluene at 65℃; for 3h; | |
97 %Spectr. | With tris(bis(trimethylsilyl)amido)lanthanum(III) In neat (no solvent) at 25℃; for 12h; chemoselective reaction; | |
In tetrahydrofuran at 60℃; for 2h; Inert atmosphere; | 2 0024] Example 2: [Lph Li4 (THF) 4] 2 catalyzes the reduction reaction of propylene carbonate and pinacol borane Under an inert atmosphere, add 5.84 mg of catalyst to the reaction flask after dehydration and deoxygenation, and add propylene carbonate (42.4 uL, 0.5 mmol) and pinacol borane (239.4 uL, 1.65 mmol) with a pipette. , THF (200 uL), react at 60 oC for 120 min, use mesitylene (69.6 uL, 0.5 mmol) as the internal standard, stir evenly, pipette a drop into the nuclear magnet tube, add CDCl3 to make a solution. The calculated yield of 1H spectrum is 99%. | |
95 %Spectr. | With manganese(II) bis(trimethylsilyl)amide In benzene-d6 at 20℃; for 20h; Inert atmosphere; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42.8 %Spectr. | With C24H16AlClN2O2 at 25℃; for 36h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 7 %Chromat. 2: 13 %Chromat. | With hydrogen; sodium nitrite at 160℃; for 2h; Autoclave; | 2.4. Catalytic tests General procedure: All the RH and NARO reactions were carried out together ina 100 mL autoclave reactor with a magnetic stirrer and an electricalheater (Fig. 1). In a typical procedure, 15 mmol of aromaticamine, 7.5 mmol of carbonate, 0.075 mmol of Ru-based catalyst,0.375 mmol of metal salts as promotor, and 10 mL of isopropanol(IPA) were put into the autoclave together with a magnetic bar.0.5 mL of isooctane was put into the reactor as an internal standardfor a quantitative analysis. The reactor was purged with hydrogenthree times to remove any remaining air, followed by pressurizingthe reactor with hydrogen gas up to 4 MPa. The reactor wasthen heated to a specific temperature with addition of hydrogengas to 8.3 MPa. The pressure was maintained constantly using areservoir tank equipped with a high-pressure regulator and a pressuretransducer to monitor pressure drop during the reaction. Aftercompletion of the reaction, the reactor was cooled to RT and thereaction mixture was filtered off to remove catalyst for furtherreaction. The resulting solution was analyzed on Agilent 6890N gaschromatograph equipped with a flame ionization detector and onan Agilent 6890N-5975 MSD-GC Mass spectrometer equipped withHP-5 column (30 m×0.32 m×0.25 m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.9% | With sodium ethanolate In ethanol at 80℃; for 8h; | 1.1; 2.1 (1) Preparation of PPP Add 200 ml of ethanol and 37.25 g of 4-phenoxyphenol (0.2 mol) to a 500 ml reaction flask. After heating and stirring to dissolve, add 1.02 g (0.015 mol) of sodium ethoxide and 30.6 g (0.30 mol) of propylene carbonate.Heat to 80°C and reflux, keep warm and react for 8 hours.Liquid chromatography detected that the 4-phenoxyphenol reaction was complete. Cool to room temperature, distill ethanol and excess propylene carbonate to dryness under reduced pressure.Add 100 ml of saturated brine and 150 ml of toluene, stir for 15 minutes, and then stand for separation. Separate the organic phase and dry with anhydrous sodium sulfate.After filtration, the filtrate was distilled under reduced pressure to recover the toluene solvent to dryness.The residue was recrystallized with isopropanol to obtain 45.39 g of white crystalline powder, with a content of 99.12% (checked by liquid chromatography), and a yield of 92.90% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrabutyl ammonium fluoride; (R,R)-bis(bis(3,5-trifluoromethylphenyl)ureido)-(salen)aluminum In neat (no solvent) at 20 - 90℃; for 3h; Schlenk technique; Sealed tube; | 1 bar of CO2 and 45 °C reaction condition General procedure: 5000 equiv. of dried oxirane (47.0 mmol) was placed in a Teflon capped Schlenk flask, 1 equiv. (0.009 mmol) ofcatalyst and 1 equiv. (0.009 mmol) of ammonium halide were added to the flask. The mixture was degassed by lyophilization3 times. The degassed mixture was heated up to room temperature. Dried CO2 was packed in the flask andTeflon cap was closed. The mixture in flask was stirred for 3 hours at 45 °C. After stirred, the reaction mixture wascooled down to room temperature and filtered over silica-gel (5 cm) with DCM. The filtrate was concentrated underreduced pressure. Clear or off yellow oil was prepared. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With dmap at 180℃; for 24h; Glovebox; Sealed tube; Inert atmosphere; | 1-11 Example 3 Transfer the flame-dried 250mL three-necked round bottom flask to the glove box, add 4-dimethylaminopyridine (DMAP) (1.46g, 12mmol) and propylene carbonate PC (122.21g, 1.2mol) in sequence, and seal the round bottom flask. Then transfer to the oil bath,Then connect the round-bottomed flask with a condenser tube with a branch pipe and an argon gas inlet/outlet device, quickly ventilate more than three times, and adjust the gas flow rate to stably blow argon gas into the reaction solution (flow rate is 5.0mL /min).Then began to slowly raise the temperature to 180°C, react for 24h,Fractionate the distillate received at the branch port of the condenser,Receiving the fraction at 40-120°C is the target product allyl alcohol. The rate is about 85%, Purity>99% (determined by 1H NMR results). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: 1,2-propylene cyclic carbonate; 3-(4-hydroxyphenyl)propionic acid methyl ester With potassium carbonate In neat (no solvent) at 160℃; for 1h; Inert atmosphere; Stage #2: With sodium hydroxide Reflux; |
Tags: 108-32-7 synthesis path| 108-32-7 SDS| 108-32-7 COA| 108-32-7 purity| 108-32-7 application| 108-32-7 NMR| 108-32-7 COA| 108-32-7 structure
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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 |
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