* 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.
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.
Reference：
[1] Journal of Molecular Catalysis A: Chemical, 2014, vol. 385, p. 133 - 140
[2] Journal of Catalysis, 2004, vol. 227, # 2, p. 537 - 541
[3] Green Chemistry, 2017, vol. 19, # 16, p. 3908 - 3915
[4] Chemische Berichte, 1986, vol. 119, # 3, p. 1090 - 1094
[5] Tetrahedron Letters, 2008, vol. 49, # 46, p. 6589 - 6592
2
[ 124-38-9 ]
[ 75-56-9 ]
[ 51260-39-0 ]
[ 16606-55-6 ]
Yield
Reaction Conditions
Operation in experiment
34.2%
With C126H91CoN12O10; tetrabutyl-ammonium chloride In dichloromethane at 25℃; for 96 h; Autoclave
General procedure: All reactions were conducted in a 100 mL stainless steel autoclave equipped with a magnetic stir bar, and submerged in anoil bath. The required catalyst, tetrabutylammonium chloride (TBAC) as the co‐catalyst, epoxide, and CH2Cl2 were added tothe reactor in turn. The reactor was then charged with CO2 and vented three times, and finally pressurized with CO2 to 1.0 MPa. The contents were then stirred at room temperature for an established period that depended on the selected substrate and catalyst, after which the reactor was carefully discharged to atmospheric pressure. The yield of cyclic carbonate was determinedby the subtraction method or by comparison betweenthe integral areas obtained by 1H NMR spectroscopy for thecyclic carbonate and epoxide.
31.6%
With C126H91CoN12O10; tetrabutyl-ammonium chloride In dichloromethane at 25℃; for 96 h; Autoclave
General procedure: All reactions were conducted in a 100 mL stainless steel autoclave equipped with a magnetic stir bar, and submerged in anoil bath. The required catalyst, tetrabutylammonium chloride (TBAC) as the co‐catalyst, epoxide, and CH2Cl2 were added tothe reactor in turn. The reactor was then charged with CO2 and vented three times, and finally pressurized with CO2 to 1.0 MPa. The contents were then stirred at room temperature for an established period that depended on the selected substrate and catalyst, after which the reactor was carefully discharged to atmospheric pressure. The yield of cyclic carbonate was determinedby the subtraction method or by comparison betweenthe integral areas obtained by 1H NMR spectroscopy for thecyclic carbonate and epoxide.
38.8 % ee
at 25℃; for 25 h; Autoclave
General procedure: A solution of freshly prepared SalenCo(III)Y (0.1 mmol) andepoxide (100 mmol) was introduced into a 100 mL stainless-steelautoclave, which was purged three times and charged with CO2to 1.2 MPa. The reaction mixture was stirred at room temperature.When the pressure of reactor was fall down to a presetting value, itwas then vented carefully. After removing the excess epoxide, theresidue was weighed to measure the conversion of epoxide, chiralcyclic carbonate (R = Me, Et, CH2Cl) was distilled under vacuum as asa colorless liquid or it (R = Ph, PhOCH2) was obtained by columnchromatography through a short silica–gel column to yield whitesolid product (ethyl acetate/petroleum ether = 5:1).
Reference：
[1] Dalton Transactions, 2013, vol. 42, # 27, p. 9930 - 9937
[2] Chinese Journal of Catalysis, 2018, vol. 39, # 5, p. 997 - 1003
[3] Chinese Journal of Catalysis, 2018, vol. 39, # 5, p. 997 - 1003
[4] Journal of the American Chemical Society, 2004, vol. 126, # 12, p. 3732 - 3733
[5] Chemical Communications, 2004, # 14, p. 1622 - 1623
[6] Tetrahedron Letters, 2007, vol. 48, # 2, p. 297 - 300
[7] Tetrahedron Letters, 2008, vol. 49, # 46, p. 6589 - 6592
[8] Advanced Synthesis and Catalysis, 2009, vol. 351, # 9, p. 1325 - 1332
[9] Advanced Synthesis and Catalysis, 2009, vol. 351, # 9, p. 1325 - 1332
[10] Green Chemistry, 2009, vol. 11, # 7, p. 935 - 938
[11] Green Chemistry, 2009, vol. 11, # 7, p. 935 - 938
[12] Science China Chemistry, 2011, vol. 54, # 7, p. 1044 - 1050
[13] Science China Chemistry, 2011, vol. 54, # 7, p. 1044 - 1050
[14] Catalysis Science and Technology, 2013, vol. 3, # 10, p. 2661 - 2667
[15] Journal of Molecular Catalysis A: Chemical, 2016, vol. 411, p. 34 - 39
[16] RSC Advances, 2016, vol. 6, # 4, p. 3243 - 3249
[17] Chemical Communications, 2017, vol. 53, # 79, p. 10930 - 10933
[18] Chemical Communications, 2017, vol. 53, # 79, p. 10930 - 10933
[19] Chinese Journal of Catalysis, 2018, vol. 39, # 5, p. 997 - 1003
3
[ 124-38-9 ]
[ 75-56-9 ]
[ 51260-39-0 ]
[ 15448-47-2 ]
[ 16606-55-6 ]
Yield
Reaction Conditions
Operation in experiment
66.7 % ee
at 25℃; for 8 h; Autoclave
General procedure: Catalyst of (S,R,R,S)-ZSS-2b (631 mg, 0.1 mmol), cocatalyst of tetrabutylammonium fluoride (TBAF, 0.0522 g, 0.2 mmol), and racemic propylene oxide (PO, 7 mL, 100 mmol) were introduced into a 100-mL stainless steel autoclave to form a brown solution. The reactor was purged thrice with carbon dioxide, and charged it to 0.8 MPa. Then, the asymmetric catalytic reaction took place at room temperature. After some time, the pressure in the reactor decreased to an expected value, and it was vented to terminate the reaction. After removing the unreacted epoxide, chiral cyclic carbonate (R=Me, Et, CH2Cl), weighed to calculate the yield of cyclic carbonate, was distilled under vacuum as a colorless liquid or it (R=Ph, PhOCH2) was obtained by column chromatography through a short silica gel column (ethyl acetate:petroleum ether = 5:1).
General procedure: Catalyst of (S,R,R,S)-ZSS-2b (631 mg, 0.1 mmol), cocatalyst of tetrabutylammonium fluoride (TBAF, 0.0522 g, 0.2 mmol), and racemic propylene oxide (PO, 7 mL, 100 mmol) were introduced into a 100-mL stainless steel autoclave to form a brown solution. The reactor was purged thrice with carbon dioxide, and charged it to 0.8 MPa. Then, the asymmetric catalytic reaction took place at room temperature. After some time, the pressure in the reactor decreased to an expected value, and it was vented to terminate the reaction. After removing the unreacted epoxide, chiral cyclic carbonate (R=Me, Et, CH2Cl), weighed to calculate the yield of cyclic carbonate, was distilled under vacuum as a colorless liquid or it (R=Ph, PhOCH2) was obtained by column chromatography through a short silica gel column (ethyl acetate:petroleum ether = 5:1).
With C126H91CoN12O10; tetrabutyl-ammonium chloride In dichloromethane at 25℃; for 96 h; Autoclave
General procedure: All reactions were conducted in a 100 mL stainless steel autoclave equipped with a magnetic stir bar, and submerged in anoil bath. The required catalyst, tetrabutylammonium chloride (TBAC) as the co‐catalyst, epoxide, and CH2Cl2 were added tothe reactor in turn. The reactor was then charged with CO2 and vented three times, and finally pressurized with CO2 to 1.0 MPa. The contents were then stirred at room temperature for an established period that depended on the selected substrate and catalyst, after which the reactor was carefully discharged to atmospheric pressure. The yield of cyclic carbonate was determinedby the subtraction method or by comparison betweenthe integral areas obtained by 1H NMR spectroscopy for thecyclic carbonate and epoxide.
31.6%
With C126H91CoN12O10; tetrabutyl-ammonium chloride In dichloromethane at 25℃; for 96 h; Autoclave
General procedure: All reactions were conducted in a 100 mL stainless steel autoclave equipped with a magnetic stir bar, and submerged in anoil bath. The required catalyst, tetrabutylammonium chloride (TBAC) as the co‐catalyst, epoxide, and CH2Cl2 were added tothe reactor in turn. The reactor was then charged with CO2 and vented three times, and finally pressurized with CO2 to 1.0 MPa. The contents were then stirred at room temperature for an established period that depended on the selected substrate and catalyst, after which the reactor was carefully discharged to atmospheric pressure. The yield of cyclic carbonate was determinedby the subtraction method or by comparison betweenthe integral areas obtained by 1H NMR spectroscopy for thecyclic carbonate and epoxide.
38.8 % ee
at 25℃; for 25 h; Autoclave
General procedure: A solution of freshly prepared SalenCo(III)Y (0.1 mmol) andepoxide (100 mmol) was introduced into a 100 mL stainless-steelautoclave, which was purged three times and charged with CO2to 1.2 MPa. The reaction mixture was stirred at room temperature.When the pressure of reactor was fall down to a presetting value, itwas then vented carefully. After removing the excess epoxide, theresidue was weighed to measure the conversion of epoxide, chiralcyclic carbonate (R = Me, Et, CH2Cl) was distilled under vacuum as asa colorless liquid or it (R = Ph, PhOCH2) was obtained by columnchromatography through a short silica–gel column to yield whitesolid product (ethyl acetate/petroleum ether = 5:1).
Reference：
[1] Dalton Transactions, 2013, vol. 42, # 27, p. 9930 - 9937
[2] Chinese Journal of Catalysis, 2018, vol. 39, # 5, p. 997 - 1003
[3] Chinese Journal of Catalysis, 2018, vol. 39, # 5, p. 997 - 1003
[4] Journal of the American Chemical Society, 2004, vol. 126, # 12, p. 3732 - 3733
[5] Chemical Communications, 2004, # 14, p. 1622 - 1623
[6] Tetrahedron Letters, 2007, vol. 48, # 2, p. 297 - 300
[7] Tetrahedron Letters, 2008, vol. 49, # 46, p. 6589 - 6592
[8] Advanced Synthesis and Catalysis, 2009, vol. 351, # 9, p. 1325 - 1332
[9] Advanced Synthesis and Catalysis, 2009, vol. 351, # 9, p. 1325 - 1332
[10] Green Chemistry, 2009, vol. 11, # 7, p. 935 - 938
[11] Green Chemistry, 2009, vol. 11, # 7, p. 935 - 938
[12] Science China Chemistry, 2011, vol. 54, # 7, p. 1044 - 1050
[13] Science China Chemistry, 2011, vol. 54, # 7, p. 1044 - 1050
[14] Catalysis Science and Technology, 2013, vol. 3, # 10, p. 2661 - 2667
[15] Journal of Molecular Catalysis A: Chemical, 2016, vol. 411, p. 34 - 39
[16] RSC Advances, 2016, vol. 6, # 4, p. 3243 - 3249
[17] Chemical Communications, 2017, vol. 53, # 79, p. 10930 - 10933
[18] Chemical Communications, 2017, vol. 53, # 79, p. 10930 - 10933
[19] Chinese Journal of Catalysis, 2018, vol. 39, # 5, p. 997 - 1003
9
[ 124-38-9 ]
[ 75-56-9 ]
[ 51260-39-0 ]
[ 15448-47-2 ]
[ 16606-55-6 ]
Yield
Reaction Conditions
Operation in experiment
66.7 % ee
at 25℃; for 8 h; Autoclave
General procedure: Catalyst of (S,R,R,S)-ZSS-2b (631 mg, 0.1 mmol), cocatalyst of tetrabutylammonium fluoride (TBAF, 0.0522 g, 0.2 mmol), and racemic propylene oxide (PO, 7 mL, 100 mmol) were introduced into a 100-mL stainless steel autoclave to form a brown solution. The reactor was purged thrice with carbon dioxide, and charged it to 0.8 MPa. Then, the asymmetric catalytic reaction took place at room temperature. After some time, the pressure in the reactor decreased to an expected value, and it was vented to terminate the reaction. After removing the unreacted epoxide, chiral cyclic carbonate (R=Me, Et, CH2Cl), weighed to calculate the yield of cyclic carbonate, was distilled under vacuum as a colorless liquid or it (R=Ph, PhOCH2) was obtained by column chromatography through a short silica gel column (ethyl acetate:petroleum ether = 5:1).
General procedure: Catalyst of (S,R,R,S)-ZSS-2b (631 mg, 0.1 mmol), cocatalyst of tetrabutylammonium fluoride (TBAF, 0.0522 g, 0.2 mmol), and racemic propylene oxide (PO, 7 mL, 100 mmol) were introduced into a 100-mL stainless steel autoclave to form a brown solution. The reactor was purged thrice with carbon dioxide, and charged it to 0.8 MPa. Then, the asymmetric catalytic reaction took place at room temperature. After some time, the pressure in the reactor decreased to an expected value, and it was vented to terminate the reaction. After removing the unreacted epoxide, chiral cyclic carbonate (R=Me, Et, CH2Cl), weighed to calculate the yield of cyclic carbonate, was distilled under vacuum as a colorless liquid or it (R=Ph, PhOCH2) was obtained by column chromatography through a short silica gel column (ethyl acetate:petroleum ether = 5:1).
With C126H91CoN12O10; tetrabutyl-ammonium chloride; In dichloromethane; at 25℃; under 7500.75 Torr; for 96h;Autoclave;
General procedure: All reactions were conducted in a 100 mL stainless steel autoclave equipped with a magnetic stir bar, and submerged in anoil bath. The required catalyst, tetrabutylammonium chloride (TBAC) as the co-catalyst, epoxide, and CH2Cl2 were added tothe reactor in turn. The reactor was then charged with CO2 and vented three times, and finally pressurized with CO2 to 1.0 MPa. The contents were then stirred at room temperature for an established period that depended on the selected substrate and catalyst, after which the reactor was carefully discharged to atmospheric pressure. The yield of cyclic carbonate was determinedby the subtraction method or by comparison betweenthe integral areas obtained by 1H NMR spectroscopy for thecyclic carbonate and epoxide.
31.6%
With C126H91CoN12O10; tetrabutyl-ammonium chloride; In dichloromethane; at 25℃; under 7500.75 Torr; for 96h;Autoclave;
General procedure: All reactions were conducted in a 100 mL stainless steel autoclave equipped with a magnetic stir bar, and submerged in anoil bath. The required catalyst, tetrabutylammonium chloride (TBAC) as the co-catalyst, epoxide, and CH2Cl2 were added tothe reactor in turn. The reactor was then charged with CO2 and vented three times, and finally pressurized with CO2 to 1.0 MPa. The contents were then stirred at room temperature for an established period that depended on the selected substrate and catalyst, after which the reactor was carefully discharged to atmospheric pressure. The yield of cyclic carbonate was determinedby the subtraction method or by comparison betweenthe integral areas obtained by 1H NMR spectroscopy for thecyclic carbonate and epoxide.
With C62H97CoN6O4(2+)*2Cl(1-); at 25℃; under 9000.9 Torr; for 25h;Autoclave;Catalytic behavior;
General procedure: A solution of freshly prepared SalenCo(III)Y (0.1 mmol) andepoxide (100 mmol) was introduced into a 100 mL stainless-steelautoclave, which was purged three times and charged with CO2to 1.2 MPa. The reaction mixture was stirred at room temperature.When the pressure of reactor was fall down to a presetting value, itwas then vented carefully. After removing the excess epoxide, theresidue was weighed to measure the conversion of epoxide, chiralcyclic carbonate (R = Me, Et, CH2Cl) was distilled under vacuum as asa colorless liquid or it (R = Ph, PhOCH2) was obtained by columnchromatography through a short silica-gel column to yield whitesolid product (ethyl acetate/petroleum ether = 5:1).
With C82H71CoN12O6; tetrabutyl-ammonium chloride; In dichloromethane; at 25℃; under 7500.75 Torr; for 71h;Autoclave;
General procedure: All reactions were conducted in a 100 mL stainless steel autoclave equipped with a magnetic stir bar, and submerged in anoil bath. The required catalyst, tetrabutylammonium chloride (TBAC) as the co-catalyst, epoxide, and CH2Cl2 were added tothe reactor in turn. The reactor was then charged with CO2 and vented three times, and finally pressurized with CO2 to 1.0 MPa. The contents were then stirred at room temperature for an established period that depended on the selected substrate and catalyst, after which the reactor was carefully discharged to atmospheric pressure. The yield of cyclic carbonate was determinedby the subtraction method or by comparison betweenthe integral areas obtained by 1H NMR spectroscopy for thecyclic carbonate and epoxide.
With tetrabutyl ammonium fluoride; at 25℃; under 6000.6 Torr; for 8h;Autoclave;
General procedure: Catalyst of (S,R,R,S)-ZSS-2b (631 mg, 0.1 mmol), cocatalyst of tetrabutylammonium fluoride (TBAF, 0.0522 g, 0.2 mmol), and racemic propylene oxide (PO, 7 mL, 100 mmol) were introduced into a 100-mL stainless steel autoclave to form a brown solution. The reactor was purged thrice with carbon dioxide, and charged it to 0.8 MPa. Then, the asymmetric catalytic reaction took place at room temperature. After some time, the pressure in the reactor decreased to an expected value, and it was vented to terminate the reaction. After removing the unreacted epoxide, chiral cyclic carbonate (R=Me, Et, CH2Cl), weighed to calculate the yield of cyclic carbonate, was distilled under vacuum as a colorless liquid or it (R=Ph, PhOCH2) was obtained by column chromatography through a short silica gel column (ethyl acetate:petroleum ether = 5:1).
With tetrabutyl ammonium fluoride; at 0℃; under 6000.6 Torr; for 8h;Autoclave;
General procedure: Catalyst of (S,R,R,S)-ZSS-2b (631 mg, 0.1 mmol), cocatalyst of tetrabutylammonium fluoride (TBAF, 0.0522 g, 0.2 mmol), and racemic propylene oxide (PO, 7 mL, 100 mmol) were introduced into a 100-mL stainless steel autoclave to form a brown solution. The reactor was purged thrice with carbon dioxide, and charged it to 0.8 MPa. Then, the asymmetric catalytic reaction took place at room temperature. After some time, the pressure in the reactor decreased to an expected value, and it was vented to terminate the reaction. After removing the unreacted epoxide, chiral cyclic carbonate (R=Me, Et, CH2Cl), weighed to calculate the yield of cyclic carbonate, was distilled under vacuum as a colorless liquid or it (R=Ph, PhOCH2) was obtained by column chromatography through a short silica gel column (ethyl acetate:petroleum ether = 5:1).
With sodium methylate In methanol at 60 - 115℃; for 25h;
1.1; 1.2; 1.3; 1.4; 1.5 Example 1 Synthesis method of (S)-propylene carbonate
(1) Feeding800 kg of S-propylene glycol, 1600 kg of dimethyl carbonate and 8 kg of sodium methoxide solution were added to the reaction vessel, and heating and stirring were started.The sodium methoxide solution is a 30% sodium methoxide/methanol solution;The S-propanediol has a propylene glycol content of 99.5%, a moisture content of 0.5%, and a specific rotation of ≥16.80-17. (2) Temperature rise reactionFirst stage heating reaction The temperature is raised to 60-65 ° C, at which time a solution (mainly methanol, a small portion of dimethyl carbonate) is distilled off, received in the receiving tank, and the solution is evaporated; Second stage heating reactionThereafter, after about 12 hours, the temperature is raised from 65 ° C to 90 ° C, the solution is kept distilled, and the product is distilled as a by-product alcohol-based fuel (methanol and dimethyl carbonate); Third stage temperature rise reactionHeating was continued, and the temperature was raised from 90 ° C to 115 ° C for 8 hours, and the heating was stopped. (3) Cooling downThe temperature was lowered from 115 ° C to 60 ° C. The temperature in the reaction vessel is ≤90 ° C, and the alcohol-based fuel (mixed solution of methanol and dimethyl carbonate) is distilled off; most of the steam distilled out at >90 ° C is dimethyl carbonate, and a small amount of methanol is used as a reaction raw material for recovery. (4) Decompression reaction under reduced pressureStart decompression under reduced pressure, using vacuum distillation, vacuum degree ≥ -0.08mpa, the temperature rises at a rate of 0.2 ° C per minute,Continue to distill the solution (a mixture of methanol and dimethyl carbonate),Keep the solution evaporated, when the temperature rises to 120 ° C, basically no solvent comes out at this time,The pressure reduction and desolvation can be stopped, and the temperature is lowered; the remaining liquid in the reaction tank is (S)-propylene carbonate. In the crude (S)-propylene carbonate, the (S)-propylene carbonate content is 97% or more. From the start of the preparation to the preparation of the crude product, the reaction time was 25 hours. (5) Distillation reactionTransfer the remaining liquid after decompression and decompression to the rectification bottle, and turn on the heating and stirring.Vacuuming, ensuring a vacuum degree ≥ 0.1Mpa, starting the steaming before the fraction, steaming out about 100kg of the former fraction, and then transferring the finished product.The materials in the rectification tank were all distilled off, the rectification was stopped, and (S)-propylene carbonate was collected. The (S)-propylene carbonate has the following quality indicators:1. Appearance: colorless clear liquid;2, SPC chemical purity content (%): ≥ 99.8;3, SPC optical purity content (%): ≥ 99.4;4. SPC isomer content (%): ≤ 0.6;5. Moisture (%): ≤ 0.1; The yield of the finished SPC is 97%; the specific rotation is -2 to -3;
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