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CAS No. : | 102-09-0 | MDL No. : | MFCD00003037 |
Formula : | C13H10O3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ROORDVPLFPIABK-UHFFFAOYSA-N |
M.W : | 214.22 | Pubchem ID : | 7597 |
Synonyms : |
|
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 4 |
Num. H-bond acceptors : | 3.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 59.54 |
TPSA : | 35.53 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.28 cm/s |
Log Po/w (iLOGP) : | 2.53 |
Log Po/w (XLOGP3) : | 3.28 |
Log Po/w (WLOGP) : | 3.26 |
Log Po/w (MLOGP) : | 2.94 |
Log Po/w (SILICOS-IT) : | 2.45 |
Consensus Log Po/w : | 2.89 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.53 |
Solubility : | 0.0639 mg/ml ; 0.000298 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.7 |
Solubility : | 0.0426 mg/ml ; 0.000199 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -4.35 |
Solubility : | 0.00955 mg/ml ; 0.0000446 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.03 |
Signal Word: | Danger | Class: | 9 |
Precautionary Statements: | P260-P264-P273-P301+P312-P305+P351+P338-P314 | UN#: | 3077 |
Hazard Statements: | H302-H319-H372-H410 | Packing Group: | Ⅲ |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With sodium hydrogencarbonate In N,N-dimethyl-formamide for 1 h; Heating / reflux | 2,2'-Anhydro[1-(beta-D-arabinofuranosyl)-5-methyluridine] 5-Methyluridine (ribosylthymine, commercially available through Yamasa, Choshi, Japan) (72.0 g, 0.279 M), diphenylcarbonate (90.0 g, 0.420 M) and sodium bicarbonate (2.0 g, 0.024 M) were added to DMF (300 mL). The mixture was heated to reflux, with stirring, allowing the evolved carbon dioxide gas to be released in a controlled manner. After 1 hour, the slightly darkened solution was concentrated under reduced pressure. The resulting syrup was poured into diethylether (2.5 L), with stirring. The product formed a gum. The ether was decanted and the residue was dissolved in a minimum amount of methanol (ca. 400 mL). The solution was poured into fresh ether (2.5 L) to yield a stiff gum. The ether was decanted and the gum was dried in a vacuum oven (60° C. at 1 mm Hg for 24 h) to give a solid that was crushed to a light tan powder (57 g, 85percent crude yield). The NMR spectrum was consistent with the structure, contaminated with phenol as its sodium salt (ca. 5percent). The material was used as is for further reactions (or it can be purified further by column chromatography using a gradient of methanol in ethyl acetate (10-25percent) to give a white solid, mp 222-4° C.). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
17.6 %Chromat. | Stage #1: at 175℃; Inert atmosphere Stage #2: at 150 - 180℃; for 9 h; Inert atmosphere |
General procedure: The transesterification reaction was carried out in a threeneck round-bottom flask (150 mL), equipped with nitrogen inlet, magnetic stirring bar, dropping funnel and fractionating column connected to a liquid dividing head. Typically, under nitrogen atmosphere, phenol and catalyst were added into the flask. When the mixture was heated to 175 °C, DMC was added dropwise and the reaction temperature was kept at160–180 °C under refluxing condition. During the reaction procedure, an azeotrope of DMC and methanol were collected in receiver flask. After the reaction, the mixture was cooled to room temperature, the catalyst was centrifugalized and then the filtrate was analyzed. Identification analysis of the products was detected by GC–MS on a HP-6890/5973 system. The products were quantitatively analyzed by gas chromatograph (Agilent Technologies 7820A) equipped with a DB-35 capillary column (30 m × 320 μm × 0.25 μm) and a flame ionization detector (FID). The conversion and selectivity were calculated based on the phenol |
26.6 %Chromat. | Stage #1: at 175℃; Inert atmosphere Stage #2: at 150 - 180℃; for 9 h; Inert atmosphere |
General procedure: The transesterification reaction was carried out in a threeneck round-bottom flask (150 mL), equipped with nitrogen inlet, magnetic stirring bar, dropping funnel and fractionating column connected to a liquid dividing head. Typically, under nitrogen atmosphere, phenol and catalyst were added into the flask. When the mixture was heated to 175 °C, DMC was added dropwise and the reaction temperature was kept at160–180 °C under refluxing condition. During the reaction procedure, an azeotrope of DMC and methanol were collected in receiver flask. After the reaction, the mixture was cooled to room temperature, the catalyst was centrifugalized and then the filtrate was analyzed. Identification analysis of the products was detected by GC–MS on a HP-6890/5973 system. The products were quantitatively analyzed by gas chromatograph (Agilent Technologies 7820A) equipped with a DB-35 capillary column (30 m × 320 μm × 0.25 μm) and a flame ionization detector (FID). The conversion and selectivity were calculated based on the phenol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35.5% | at 205 - 215℃; for 24 h; Heating / reflux | A continuous multi-stage distillation column as shown in FIG. 1 having L = 3100 cm, D = 500 cm, L / D = 6.2, n = 30, D / d1 = 3.85, and D / d2 = 11.1 was used. In this example, as the internal, two sets of Mellapak (total theoretical number of stages 11) were installed in the upper portion, and the sieve tray having the cross-sectional area per hole of approximately 1.3 cm2 and a number of holes of approximately 250/m2 was used in the lower portion.<Reactive distillation> A mixture containing 18 percent by weight of methyl phenyl carbonate that had been obtained by subjecting a mixture containing dimethyl carbonate and phenol in a weight ratio of dimethyl carbonate / phenol = 1.3 to a transesterification reaction was used as a starting material. This starting material contained 26 percent by weight of dimethyl carbonate, 6 percent by weight of anisole, 48 percent by weight of phenol, and 1 percent by weight of diphenyl carbonate, and further contained approximately 100 ppm of Pb(OPh)2 as a catalyst. The starting material substantially did not contain halogens (outside the detection limit for the ion chromatography, i.e. 1 ppb or less). The starting material was introduced into the continuous multi-stage distillation column at a flow rate of 66 ton/hr from a starting material inlet installed between the Mellapak and the sieve tray. Reactive distillation was carried out continuously under conditions of a temperature at the bottom of the column being 210°C, a pressure at the top of the column being 3.x.104 Pa, and a reflux ratio being 0.3. It was possible to attain stable steady state operation after 24 hours. The liquid continuously withdrawn from the bottom of the column contained 38.4 percent by weight of methyl phenyl carbonate and 55.6 percent by weight of diphenyl carbonate. It was found that the amount of diphenyl carbonate produced from the methyl phenyl carbonate per hour was 5.13 tons. The selectivity for the diphenyl carbonate based on the methyl phenyl carbonate reacted was 99percent. Prolonged continuous operation was carried out under these conditions. The amounts of diphenyl carbonate produced per hour at 500 hours, 2000 hours, 4000 hours, 5000 hours, and 6000 hours after attaining stable steady state (excluding the diphenyl carbonate contained in the starting material) were 5.13 tons, 5.13 tons, 5.14 tons, 5.14 tons, and 5.13 tons respectively, and the selectivities were 99percent, 99percent, 99percent, 99percent, and 99percent respectively, and hence the operation was very stable. Moreover, the aromatic carbonates produced substantially did not contain halogens (1 ppb or less).; Reactive distillation was carried out under the following conditions using the same continuous multi-stage distillation column as in Example 1.<Reactive distillation> A mixture containing 21 percent by weight of methyl phenyl carbonate that had been obtained by subjecting a mixture containing dimethyl carbonate and phenol in a weight ratio of dimethyl carbonate / phenol = 1.9 to a transesterification reaction was used as a starting material. This starting material contained 32 percent by weight of dimethyl carbonate, 5 percent by weight of anisole, 41 percent by weight of phenol, and 1 percent by weight of diphenyl carbonate, and further contained approximately 250 ppm of Pb(OPh)2 as a catalyst. The starting material substantially did not contain halogens (outside the detection limit for the ion chromatography, i.e. 1 ppb or less). The starting material was introduced into the continuous multi-stage distillation column at a flow rate of 80 ton/hr from a starting material inlet installed between the Mellapak and the sieve tray. Reactive distillation was carried out continuously under conditions of a temperature at the bottom of the column being 205°C, a pressure at the top of the column being 2.x.104 Pa, and a reflux ratio being 0.5. It was possible to attain stable steady state operation after 24 hours. The liquid continuously withdrawn from the bottom of the column contained 36.2 percent by weight of methyl phenyl carbonate and 60.8 percent by weight of diphenyl carbonate. It was found that the amount of diphenyl carbonate produced from the methyl phenyl carbonate per hour was 8.06 tons. The selectivity for the diphenyl carbonate based on the methyl phenyl carbonate reacted was 99percent. Prolonged continuous operation was carried out under these conditions. The amounts of diphenyl carbonate produced per hour at 500 hours, 1000 hours, 1500 hours, 2000 hours, and 2500 hours after attaining stable steady state (excluding the diphenyl carbonate contained in the starting material) were 8.06 tons, 8.07 tons, 8.07 tons, 8.06 tons, and 8.07 tons respectively, and the selectivities were 99percent, 99percent, 99percent, 99percent, and 99percent respectively, and hence the operation was very stable. Moreover, the aromatic carbonates produced substantially did not contain halogens (1 ppb or less).; Reactive distillation was carried out under the following conditions using the same continuous multi-stage distillation column as in Example 1, except that the cross-sectional area per hole of the sieve tray was made to be approximately 1.8 cm2.<Reactive distillation> A mixture containing 16 percent by weight of methyl phenyl carbonate that had been obtained by subjecting a mixture containing dimethyl carbonate and phenol in a weight ratio of dimethyl carbonate / phenol = 1.4 to a transesterification reaction was used as a starting material. This starting material contained 27 percent by weight of dimethyl carbonate, 7 percent by weight of anisole, 49 percent by weight of phenol, and 0.5 percent by weight of diphenyl carbonate, and further contained approximately 200 ppm of Pb(OPh)2 as a catalyst. The starting material substantially did not contain halogens (outside the detection limit for the ion chromatography, i.e. 1 ppb or less). The starting material was introduced into the continuous multi-stage distillation column at a flow rate of 94 ton/hr from a starting material inlet installed between the Mellapak and the sieve tray. Reactive distillation was carried out continuously under conditions of a temperature at the bottom of the column being 215°C, a pressure at the top of the column being 2.5.x.104 Pa, and a reflux ratio being 0.4. It was possible to attain stable steady state operation after 24 hours. The liquid continuously withdrawn from the bottom of the column contained 35.5 percent by weight of methyl phenyl carbonate and 59.5 percent by weight of diphenyl carbonate. It was found that the amount of diphenyl carbonate produced from the methyl phenyl carbonate per hour was 7.28 tons. The selectivity for the diphenyl carbonate based on the methyl phenyl carbonate reacted was 99percent. Prolonged continuous operation was carried out under these conditions. The amounts of diphenyl carbonate produced per hour at 500 hours, 1000 hours, 1500 hours, 2000 hours, and 2500 hours after attaining stable steady state (excluding the diphenyl carbonate contained in the starting material) were 7.28 tons, 7.28 tons, 7.29 tons, 7.29 tons, and 7.28 tons respectively, and the selectivities were 99percent, 99percent, 99percent, 99percent, and 99percent respectively, and hence the operation was very stable. Moreover, the aromatic carbonates produced substantially did not contain halogens (1 ppb or less).Industrial Applicability When continuously producing aromatic carbonates containing a diaryl carbonate as a main product by taking an alkyl aryl carbonate as a starting material, which is obtainable through a transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound, using a continuous multi-stage distillation column in which a catalyst is present, and continuously feeding the starting material into the continuous multi-stage distillation column, the present invention is suitable as a specific process that enables the diaryl carbonate to be produced with high selectivity and high productivity stably for a prolonged period of time on an industrial scale of not less than 1 ton per hour. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.82% | at 129.2 - 214℃; | EXAMPLE 1 An Aspen model depicting the process as shown in Figure 1 was developed and run using Aspen Plus 11.1 simulation software and the results are indicated in Table 1 wherein the reactants used were dimethyl carbonate and phenol in the presence of titaniumtetraphenoxide to produce diphenyl carbonate and anisole. The simulation was run using the feed molar ratio of dimethyl carbonate to phenol of 2.5. EXAMPLE 2 An Aspen model depicting the process as shown in Figure 2 was developed and run using Aspen 11.2 simulation software and the results are indicated in Table 1. The feed rnolar ratio of dimethyl carbonate and phenol was the same as in Example 1. EXAMPLES 3-17 Keeping the process conditions of Example 1, the Aspen model was run by varying the reflux ratio of column 110 from 0.83 to 1.0. The results showing the anisole purity (in weight percent) in stream 142 by changing the reflux ratio in column 110 is shown in Table 2. Fig. 3 also shows the graphical representation of the data in table 2. It shows that as the reflux ratio is increased the purity of anisole in stream 142 increases. EXAMPLE 18 A cornparative example was run by developing an Aspen model flow sheet based on a configuration wherein the anisole rich stream is drawn from the side of the second reactive distillation column. All other process conditions were same as in Example 1 and 2. The results show that in both the process options of the disclosed methods as depicted in Fig. 1 and 2, the anisole purity in stream 142 is more than what is achieved by drawing the anisole rich stream from side of second reactive distillation column under similar process conditions. Furthermore a comparison of the steam consumption predicted by Aspen simulation model of all the processes is also shown in Table 1. The comparative Example 18 where the anisole rich stream is drawn from the side of the second reactive distillation column, shows maximum steam consumption of 5.40 ton per ton of diphenyl carbonate produced whereas the disclosed methods as shown in two embodiments in Fig. 1 and Fig. 2 show steam consumption of 5.20 and 5.10 tons per ton of diphenyl carbonate produced respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With mixed-acid; sulfuric acid; nitric acid In cyclohexane; ethyl acetate; nitrobenzene | Example 1 Nitration of diphenyl carbonate in the presence of nitrobenzene. A 2000 ml reactor equipped with a mechanical stirrer, thermometer, and a jacketed addition funnel was charged with 107.11 g of diphenyl carbonate (0.5 mol) and 500 ml of nitrobenzene. The mixture was stirred until dissolution was complete. In the meantime, the mixed acid reagent was prepared by mixing 99.02 g of concentrated nitric acid and 125 ml of concentrated sulfuric acid in a beaker with cooling. The cooled mixed-acid reagent was then poured into the jacketed addition funnel and further cooled with ice. After the diphenyl carbonate had dissolved in the reaction vessel, the temperature was adjusted to 20° C. with an ice/water bath. The mixed-acid reagent was added at a rate which maintained the temperature of the reaction mixture at close to 20° C. The total addition took around 60 min. Following the addition, the reaction was stirred for an additional 60 min. The reaction mixture was then poured over 600 ml of ice/water. A 600 ml portion of ethyl acetate was added and the mixture transferred to a separatory funnel and shaken. The organic layer was removed and the aqueous layer was washed 3 times with 100 ml portions of ethyl acetate. The organic layers were combined and washed with 200 ml of saturated sodium bicarbonate and 200 ml of saturated brine. The organic layer was then dried over sodium sulfate. After the reaction mixture was dried, the ethyl acetate was removed by rotatory evaporation. The nitrobenzene solution of crude product was poured into 2000 ml of cyclohexane and the precipitated crude product (215.16 g) recovered by filtration. Gas chromatography showed the isomeric carbonates to be present in 95.6percent, 4,4'-, 0.6percent, 4,3'-, and 3.8percent, 4,2'-dinitrodiphenyl carbonate, amounts. Recrystallization from a mixture of toluene and cyclohexane resulted in 142.7 g of di(4-nitrophenyl)carbonate or a 94percent yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | at 140℃; | Example 37 In a 200 mL glass vessel equipped with an air inlet, added were 9.2 grams (106 mmol) of methacrylic acid, 44.0 grams (205 mmol) of diphenyl carbonate, 2.4 grams (12 mmol) of magnesium methacrylate as a catalyst, 0.04 grams of phenol as a polymerization inhibitor, and 3.5 grams (21 mmol) of diphenyl ether as an internal standard substance. While air was being blown into the mixture at a rate of 10 mL/min, the mixture was heated and stirred to an internal temperature of 140° C. The time when the internal temperature had reached 140° C. was set at zero, and 6.8 grams (80 mmol) of methacrylic acid was continuously added at a rate of 0.113 g/min during a time frame of 3090 minutes. Also, 5.2 grams (60 mmol) of methacrylic acid was continuously added at a rate of 0.058 g/min during a time frame of 95185 minutes. The total amount of supplied methacrylic acid was 21.2 grams (246 mmol). The mixture was stirred for an elapsed heating time of 5.0 hours. As a result, the conversion rate of diphenyl carbonate in the reaction liquid was 99.0percent. The amount of produced phenyl methacrylate was 30.9 grams (190 mmol). The yield of phenyl methacrylate relative to diphenyl carbonate was 93percent. The amount of produced MAA adduct was 0.53 grams (2.1 mmol). The yield of MAA adduct relative to diphenyl carbonate was 1.04percent. The amount of produced PhOH adduct was 0.20 grams (0.8 mmol). The yield of PhOH adduct relative to diphenyl carbonate was 0.39percent. The amount of produced phenyl methacrylate dimer was 0.79 grams (2.4 mmol). The yield of phenyl methacrylate dimer relative to diphenyl carbonate was 2.38percent. The selectivity of phenyl methacrylate (the value obtained when the yield of phenyl methacrylate is divided by the conversion rate of diphenyl carbonate) was 94percent. |
88% | at 130℃; for 16 h; | In a 200 mL glass vessel equipped with an air inlet, added were 21.2 grams (246 mmol) of methacrylic acid, 44.0 grams (205 mmol) of diphenyl carbonate, 1.2 grams (6 mmol) of magnesium methacrylate as a catalyst, 0.006 grams of 1,4-benzendiol and 0.006 grams of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl as polymerization inhibitors, and 3.5 grams (21 mmol) of diphenyl ether as an internal standard substance. While air was being blown into the mixture at a rate of 10 mL/min, the mixture was heated to an internal temperature of 100° C. and stirred for 16 hours. As a result, the conversion rate of diphenyl carbonate was 28.2percent in the reaction liquid. The amount of produced phenyl methacrylate was 8.8 grams (54 mmol). The yield of phenyl methacrylate relative to diphenyl carbonate was 27percent. In addition, the selectivity of phenyl methacrylate (the value obtained when the yield of phenyl methacrylate is divided by the conversion rate of diphenyl carbonate) |