Methyl 4-bromobenzo[b]thiophene-2-carboxylate

General procedure: To a stirred solution of compound 1a-1n (9.90 mmol) in DMF (20 mL) were added methyl thioglycolate (10.9 mmol) and potassium carbonate (39.6 mmol). The resulting mixture was stirred at 60 °C for 15 h. The DMF was removed under reduced pressure, water (50 mL) was added and the mixture was extracted with ethylacetate (2 x 40 mL). The combined organic layers were dried withsodium sulfate, filtered, and the solvents were removed under reduced pressure to afford the title compound 2a-2n [31, 34]. 4.1.1.1. Methyl 4-bromobenzo[b]thiophene-2-carboxylate (2a).Yield 89percent, white solid; m. p. 77-78 °C; 1H NMR (600 MHz, DMSO‑d6) δ 8.12 (d, J = 8.2 Hz, 1H), 8.01 (d, J = 0.6 Hz, 1H), 7.73 (d, J = 7.7 Hz, 1H), 7.46 (t, J = 7.9 Hz, 1H), 3.91 (s, 3H).12151] A mixture of 750 ng of methyl 4-bromobenzo[b] thiophene-2-carboxylate, 438mg of phenyl boronic acid, 610 mg of lithium chloride, 528mg of sodium carbonate, 160mg of tetrakis(triphenylphosphine)palladium (0), 30 ml of 1, 4- dioxane, and 15 ml of water was stirred for 4 hours at 1000 C. under nitrogen atmosphere. After being cooled to room temperature, the reaction mixture was concentrated under reduced pressure. Chloroform and water were added to the residues, and insoluble matter was separated by filtration. The aqueous layer was extracted twice by using chloroform, and the collected organic layer was washed with saturated saline, dried over magnesium sulfate, and then concentrated under reduced pressure. The residues were subjected to silica gel column chromatography, thereby obtaining 477mg of methyl 4-phenylbenzo[b]thiophene-2-carboxylate (hereinafier, described as a 'compound 34 of the present invention?).12152] Compound 34 of the Present Inventionj2153] 'H-NMR (CDC13) oe: 8.17-8.16 (m, 1H), 7.87-7.85 (m, 1H), 7.57-7.48 (m, 5H), 7.47-7.42 (m, 1H), 7.41-7.39 (m, 1H), 3.93 (s, 3H).A mixture of 750 mg of General procedure: To a stirred solution of compound 1a-1n (9.90 mmol) in DMF (20 mL) were added methyl thioglycolate (10.9 mmol) and potassium carbonate (39.6 mmol). The resulting mixture was stirred at 60 C for 15 h. The DMF was removed under reduced pressure, water (50 mL) was added and the mixture was extracted with ethylacetate (2 x 40 mL). The combined organic layers were dried withsodium sulfate, filtered, and the solvents were removed under reduced pressure to afford the title compound 2a-2n [31, 34]. 4.1.1.1. Methyl 4-bromobenzo[b]thiophene-2-carboxylate (2a).Yield 89%, white solid; m. p. 77-78 C; 1H NMR (600 MHz, DMSO-d6) delta 8.12 (d, J = 8.2 Hz, 1H), 8.01 (d, J = 0.6 Hz, 1H), 7.73 (d, J = 7.7 Hz, 1H), 7.46 (t, J = 7.9 Hz, 1H), 3.91 (s, 3H).Methyl thioglycolate (42.35 g) was added under nitrogen at 80 C. to a solution of triethylamine (109 ml) in dimethylformamide (290 ml), the mixture was stirred at 100 C. for 15 minutes, then a solution of 2-bromo-6-fluorobenzaldehyde (81.35 g; prepared in a manner similar to that described above) in dimethyl-formamide (70 ml) was added. The mixture was stirred at 130 C. for 5 hours, then it was cooled to ambient temperature and poured into ice-water (3000 ml). The resulting solid was collected by filtration, washed with water (2*250 ml) and dried in air to give To a suspension of sodium hydride (55%, 1.11 g) in dimethyl sulfoxide (20 mL) was added methyl thioglycolate (1.53 mL) at room temperature, and the mixture was stirred for 15 minutes. A solution of 2-bromo-6-fluorobenzaldehyde (3.43 g) in dimethyl sulfoxide (4mL) was added to the reaction mixture, and the mixture was stirred at room temperature for 5 minutes. The reaction mixture was poured into water with ice and precipitated crystalline solid was collected by filtration, washed with water and dried under reduced pressure to give

Molecular Weight:271.13
XLogP3:3.8
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:2
Exact Mass:269.93501
Monoisotopic Mass:269.93501
Topological Polar Surface Area:54.5
Heavy Atom Count:14
Complexity:234
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes