Dipentyl carbonate

The reaction apparatus was the same as in Example 1. 10 g of urea, 60 g of n-pentanol, 0.5 g of nickel acetate, 2 g of triphenylphosphine in a three-necked flask were placed in a 170 ° C oil bath, the system was boiled at 140 ° C, and refluxed for 20 hr. Gas chromatography analysis showed that the yield of di-n-pentyl carbonate was 92.2percent based on the amount of urea charged.General procedure: The transesterification reaction was carried out in a 50 mLround-bottomed flask, equipped with a condenser, thermostatand magnetic stirring. A calculated amount of DMC, THFA, and APC-ILs were added to the reactor, and the reaction mixturewas stirred and allowed to proceed for 0.5–2.5h with theheating at the designed temperature (e.g., 130 °C). After thereaction was completed, qualitative analyses of products wereexamined by a Thermo Trace 1300 GC-ISQ, and quantitativeanalyses were carried out by a GC-FID (Agilent 7890B)equipped with a capillary column HP-5 (methyl polysiloxane, 30 m × 0.32 mm × 1 m). The detailed analysis conditionswere described as follows: The temperatures of injector anddetector were 280 and 250 °C, respectively. The column temperaturewas increased stepwise to 200 °C, holding at 80 °Cfor 2 min, increasing to 200 °C at 40 °C min−1, holding at240 °C for 3min. Then the conversion of DMC and yield ofDTC were calculated according to the area of chromatographpeaks using 1, 3, 5-trimethylbenzene as an internal standard.After the completion of reaction, the reaction system wascooled down to room temperature and extracted with deionizedwater, and the system thus forms a liquid–liquid biphase, and the aqueous phase containing APC-ILs could be easilyseparated by simple decantation. After that, the catalyst APCILswere further heated in a vacuum oven at 90 °C for 6h toremove water and the residual reactants. The water contentof recycled APC-ILs was measured prior to the next run andchecked to be less than 0.15wtpercent by the Karl Fisher titration.General procedure: All the reactions were carried out in an autoclave reactor withan inner volume of 190 ml. A typical procedure of the reaction of COGeneral procedure: A mixture of cinnamyl alcohol (67.1 mg, 0.5mmol), Cs2CO3 (325.8 mg, 1 mmol) and 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) (0.1 mL) in dibromomethane (1 mL) was equipped with a seal tube and stirred for 18 h at 70° C. The reaction mixture was evaporated and purified by flash column chromatography (silica gel) (2percent Ether/hexane) to obtain dicinnamyl carbonate (1a) 69.0 mg (94percent).General procedure: For the synthesis of organic carbonates from cinnamyl alcohol, organic solvent and alcohol activating agent 1 mL of dichloromethane (DCM) and 0.1 mL of an ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate, bmimPF6 to the mixture was added 0.5 mM cinnamyl alcohol and 2 equivalents of cesium carbonate (Cs2CO3), which is the carbon donating source, were stirred at 70C for 18 hours. Thereafter, the reaction mixture was cooled and separated and purified by column chromatography to obtain a carbonate 1a compound. Was synthesized in the same manner as in Example 1, except that 1 mL of dibromomethane (DBM) was used instead of dichloromethane to obtain a carbonate 1a compound. On the other hand, carbonate 1a was synthesized using various alcohols and cesium carbonate, including benzyl alcohol, allyl alcohol and aliphatic alcohol, in addition to the cinnamic alcohol shown in Table 1. To the solvent was added a mixture of 0.5 mM alcohol and 1.0 mM cesium carbonate in a seal tube for 18 hours at 70C. The results are shown in Table 2.General procedure: 1) A mixture was prepared by mixing high pressure stainless steel reactor with magnetic stirrer and electric heater of 5 mmol methanol in 100 ml, 5 mmol of an imidazolium cation and a bicarbonate anion ([IL tagged Hunig base] [HCO 3]), 5 mmol Cs [Triazolide] base and 15 ml CH2Br2 solvent. 2) The mixture was purged of carbon dioxide to the reactor at 80 psi pressure. 3) The atmosphere was evacuated three times from the mixture. 4) Stir at 500 rpm, and It was heated to 50 temperature and increase the carbon dioxide pressure at 300psi. 5) The reaction was carried out for 24 hours while maintaining the carbon dioxide pressure at 300 psi to prepare dimethyl carbonate (DMC). 6) After the reaction was completed, the reaction mixture was allowed to stand at room temperature, and the resulting mixture was transferred to a vial to calculate the conversion of methanol and the yield of dimethyl carbonate using GD-FID.General procedure: The transesterification reaction was carried out in a 50 mLround-bottomed flask, equipped with a condenser, thermostatand magnetic stirring. A calculated amount of DMC, THFA, and APC-ILs were added to the reactor, and the reaction mixturewas stirred and allowed to proceed for 0.5'2.5h with theheating at the designed temperature (e.g., 130 °C). After thereaction was completed, qualitative analyses of products wereexamined by a Thermo Trace 1300 GC-ISQ, and quantitativeanalyses were carried out by a GC-FID (Agilent 7890B)equipped with a capillary column HP-5 (methyl polysiloxane, 30 m × 0.32 mm × 1 m). The detailed analysis conditionswere described as follows: The temperatures of injector anddetector were 280 and 250 °C, respectively. The column temperaturewas increased stepwise to 200 °C, holding at 80 °Cfor 2 min, increasing to 200 °C at 40 °C min'1, holding at240 °C for 3min. Then the conversion of DMC and yield ofDTC were calculated according to the area of chromatographpeaks using 1, 3, 5-trimethylbenzene as an internal standard.After the completion of reaction, the reaction system wascooled down to room temperature and extracted with deionizedwater, and the system thus forms a liquid'liquid biphase, and the aqueous phase containing APC-ILs could be easilyseparated by simple decantation. After that, the catalyst APCILswere further heated in a vacuum oven at 90 °C for 6h toremove water and the residual reactants. The water contentof recycled APC-ILs was measured prior to the next run andchecked to be less than 0.15wtpercent by the Karl Fisher titration.In a typical procedure, [N2222][Pro] (0.5 wtpercent, based on the total weight of DMC and BuOH), DMC (20 mmol) and BuOH (80 mmol)were added into a round-bottomed flask (50 mL) fitted with a magnetic stirrer and condenser. Then, the reaction mixture was vigorously stirred and allowed to proceed for 1'6 h with the heating at the designed temperature (e.g., 110 °C). After the reaction was completed, the reactor was cooled down. About 0.2 mL of liquid sample was taken from the reactor and detected by gas chromatography (GC). Subsequently, the reaction mixture was extracted with deionized water (10 mL × 3), and the system thus forms a liquid'liquid biphase, and the aqueous phase containing ILs could be easily separated by simple decantation. After that, the catalyst ILs were further in a vacuum oven at 80 °C for 12 h to remove water and the residual reactants prior to reuse in the next run. Qualitative analyses of products were examined by a Thermo Trace 1300 GC-ISQ, and quantitative analyses were carried out by a GC-FID (Agilent 7890B).The detailed analysis conditions were described as follows: the injector and detector temperatures were 250 and 250C, respectively; the column temperature was increased stepwise to 200 °C, holding at 80 °C for 2 min, increasing to 200 °C at 40 °C min'1, holding at 200 °C for 5 min. Then the conversion and selectivity were calculated according to the area of chromatograph peak usingbiphenyl as an internal standard.General procedure: A mixture of cinnamyl alcohol (67.1 mg, 0.5mmol), Cs2CO3 (325.8 mg, 1 mmol) and 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) (0.1 mL) in dibromomethane (1 mL) was equipped with a seal tube and stirred for 18 h at 70° C. The reaction mixture was evaporated and purified by flash column chromatography (silica gel) (2percent Ether/hexane) to obtain dicinnamyl carbonate (1a) 69.0 mg (94percent).The reaction apparatus was the same as in Example 1. 10 g of urea, 60 g of n-pentanol, 0.5 g of nickel acetate, 2 g of triphenylphosphine in a three-necked flask were placed in a 170 ° C oil bath, the system was boiled at 140 ° C, and refluxed for 20 hr. Gas chromatography analysis showed that the yield of di-n-pentyl carbonate was 92.2percent based on the amount of urea charged.Examples 2 to 6; Start-up operation was performed in the same manner as in the except that dialkyl carbonates of types shown in the following Table 1 were used in place of bis(3-methylbutyl)carbonate, so as to produce diphenyl carbonate (diaryl carbonate). A flow rate and a pressure were controlled depending on the type of each dialkyl carbonate in control operation.In distillation separation in a distillation column 130, a high boiling component removed from a column bottom contained about 7percent by mass, about 10percent by mass, about 8percent by mass, about 9percent by mass, and about 8percent by mass of a component having a higher boiling point than that of the diphenyl carbonate, in order of examples 2 to 6.The results of analyzing a titanium-containing high boiling component obtained from a removal line 11 are shown in Table 1. All the examples satisfied the conditions of the above-mentioned items (iv) to (vi), and could stably produce the diaryl carbonates.

Molecular Weight:202.29
XLogP3:4.1
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:10
Exact Mass:202.15689456
Monoisotopic Mass:202.15689456
Topological Polar Surface Area:35.5
Heavy Atom Count:14
Complexity:121
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes