METHYL PHENYL CARBONATE

colourless liquid

General procedure: To a solution ofalcohol (or thiol) 4 (0.7 mmol) and AlCl3 (0.7 mmol) intoluene (10 mL), compound 3 (0.7 mmol) was added. Themixture was stirred at room temperature until compound 3was consumed, as determined by TLC. A 10percent aqueousNaOH solution (50 mL) and dichloromethane (30 mL) wereadded to the reaction mixture with stirring. The organic layerwas extracted and washed water (50 mL), and dried overanhydrous magnesium sulfate, and the solvent was evaporatedunder the reduced pressure. The resulting residue wastransferred to an open-bed silica gel column (2.5 × 4 cm).The column was eluted with n-hexane/ethyl acetate (3:1, v/v) to isolate compound 5 and 6 and then ethyl acetate toisolate 4, 5-dichloropyridazin-3(2H)-one (1). The columnfractions containing pure compound were combined andevaporated under reduced pressure to give the respectiveproduct. 4, 5-Dichloropyridazin-3(2H)-one was obtainedquantitative yield and reused.General procedure: Alcohol 3 or 5 (0.84 mmol) was added to a solution of the appropriate pyridazine 1 (0.7mmol) and KOtBu (0.84 mmol) in toluene (10 mL), and the mixture was stirred at r.t. untilpyri-dazine 1 was consumed (TLC). 10percent aq NaOH (50 mL) and CH2Cl2 (30 mL) wereadded to the mixture with stirring. The organic layer was separated, washed with H2O (50mL), dried (MgSO4), and concentrated under reduced pressure. The residue was transferredto an open-bed column of silica gel (2.5 × 4 cm), which was eluted with hexane–EtOAc (3:1)to give the symmetric carbonates 2, or the asymmetric carbonates 4 or 6, and then eluted withEtOAc to isolate 4, 5-dichloropyridazin-3(2H)-one quantitatively for reuse.(2) Step (II) of continuously producing methyl phenyl carbonate General procedure: In Examples 50 and 51, transesterification reaction between dimethyl carbonate and 1-adamantanol as a tertiary alcohol was carried out under the conditions shown in Table 10 in accordance with Example 31. As a result, ester products were obtained in high yield in each case. In Examples 52 and 53, transesterification reaction of dimethyl carbonate and phenol, which is an aromatic alcohol, was carried out under the conditions shown in Table 10 in accordance with Example 31. As a result, ester products were obtained in high yield in each case. Here, since dimethyl carbonate was used as a reaction substrate and solvent, the yield was calculated based on the alcohol compound.General procedure: The same continuous reaction as used in above was carried out, except that the reaction conditions were changed as shown in Table 1 below. The reaction results are also shown in Table 1.Phenol (65.88g, 700 mmol), dimethyl carbonate (31.53g, 350 mmol) and Sm(acac)A tubular reactor with an inner volume of 80 ml is disposed in an oil bath capable of maintaining constant temperature, and then phenol (130 mmol), dimethyl carbonate (65 mmol), and 30 ppm (4 mg) of a catalyst represented by Formula id based on the weight of the dimethyl carbonate are introduced into the reactor, followed by replacing oxygen in the reactor with nitrogen, and the reactor is heated to 230° C. Next, the reactor is maintained at 230° C. for 5 minutes to form an aromatic carbonate, for example methylphenyl carbonate. The reactor is cooled to room temperature using a cooler, followed by measuring a yield of the prepared aromatic carbonate (a conversion rate of the dimethyl carbonate) through liquid chromatography. Results are shown in Table 1. An aromatic carbonate is prepared in the same manner as in Example 1, except that a dose (concentration) of the catalyst is changed as listed in Table 1. A yield ofthe prepared aromatic carbonate (a conversion rate of the dimethyl carbonate) is measured by liquid chromatography. Results are shown in Table 1.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 phenolGeneral 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 phenolA continuous multi-stage distillation column as shown in FIG. 1 having L = 3100 cm, D = 500 cm, L / D = 6.2, n = 30, D / dAn 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. 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. 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 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 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.

Molecular Weight:152.15
XLogP3:1.9
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:152.047344113
Monoisotopic Mass:152.047344113
Topological Polar Surface Area:35.5
Heavy Atom Count:11
Complexity:127
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes