2-Bromothioanisole

clear yellow liquid

Under an argon atmosphere, to a solution of NaOH (0.32 g, 7.9 mmol) in EtOH (3.0 mL) was added dropwise 2-bromobenzenethiol (1.0 g, 5.29 mmol), and the mixture was stirred for 30 min, after which CHTo a solution of NaOH (1.7 g, 42.50 mmol) in EtOH(15 mL) was added 2-bromo thiophenol (5 g, 26.45 mmol). The reaction mixture was stirred at r.t. for 30 mm beforecooling to 0°C, and methyl iodide (2.4 mL, 39 mmol) was added. The reaction mixture was stirred at r.t. for 10 h. The reaction mixture was treated with iced water, and extracted with DCM (2x 2OmL). The organic layer was washed with water and brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by flash chromatography (Si02, 0-5 percent EtOAc/hexanes), yielding the title compound as a yellow oil (4.6 g, 86percent).LCMS (ESj 203.0/205.0 (M+H).Under an argon atmosphere, In a 100 mL two-necked eggplant-shaped flask, copper (II) sulfate anhydride (95.8 mg, 0.600 mmol)Sodium bicarbonate (1.01 g, 12.0 mmol) was added.In contrast, methanol (40 mL)To a solution of p-tolylmethylthiosulfonate (9) (1.21 g, 6.00 mmol)And a solution of 2-bromophenylboronic acid (8a) (1.81 g, 9.00 mmol) were added, and the mixture was stirred at room temperature for 2 days.Water was added to the reaction mixture to stop the reaction, followed by extraction with ethyl acetate (50 mL × 3).The combined organic layer was washed with saturated brine and dried over sodium sulfate.After filtration, concentration under reduced pressure gave a crude product.This was purified by silica gel column chromatography (30 g, n-hexane only) to obtain (2-bromophenyl) methylsulfide (10a) (867 mg, 4.27 mmol, yield 71.1percent).To a mixture of NaHCO3 (1.01 g, 12.0 mmol, 2.0 equiv) and CuSO4 (95.8 mg, 0.600 mmol, 10 mol percent) wasadded a solution of S-methyl 4-toluenethiosulfonate (2) (1.21 g, 6.00 mmol) and 2-bromophenylboronic acid (1a)(1.81 g, 9.00 mmol, 1.5 equiv) dissolved in MeOH (40 mL) at room temperature. After stirring for 48 h at thesame temperature, to the mixture was added an aqueous saturated ammonium chloride solution (10 mL). Themixture was extracted with EtOAc (50 mL 3), and the combined organic extract was washed with brine (20 mL), dried (Na2SO4), and after filtration, the filtrate was concentrated under reduced pressure. The residue was purifiedby flash column chromatography (silica-gel 30 g, n-hexane) to give 2-bromophenyl methyl sulfide (867 mg, 4.27mmol, 71.1percent) as a colorless oil.

Molecular Weight:203.10
XLogP3:3.1
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:1
Exact Mass:201.94518
Monoisotopic Mass:201.94518
Topological Polar Surface Area:25.3
Heavy Atom Count:9
Complexity:85
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes