2-bromo-4-chlorobenzenethiol

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-bromo-4-chlorothiophenol (3.74 g, 16.8 mmol), p-toluene sulfonic acid (0.427 g, 1.7 mmol) and 3,4-dihydro-2-H-pyran (0.985 ml, 16.8 mmol) in CH2Cl2 (30 mL) was stirred at 23° C. for 18 hours. After the addition of NaOH, the organic phase was separated, dried over MgSO4, filtered and the filtrate was concentrated in vacuo to afford the title compound as a yellow oil, (4.91 g, 95%) 1H NMR (CDCl3) δ7.6-7.5 (m, 2H), 7.35-7.2 (m, 1H), 5.37 (t, J=4.5 Hz, SCHO, 1H), 4.25-4.1 (m, CH2O, 1H), 3.7-3.55 (m, CH2O, 1H), 2.2-2.05 (m, 1H), 2.0-1.8 (m, 2H), 1.8-1.6 (m, 3H): IR 1566, 1542, 1450, 1367, 1257, 1188, 1101, 1037, 1024, 1008, 867, 809, 783 cm−1; Anal. Calcd. for C11H12BrClOS: C, 42.95; H, 3.93. Found: C,43.15; H, 3.91. the organic phase was separated dried over MgSO4 filtered the filtrate was concentrated in vacuo

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-bromo-4-chlorothiophenol (3.74 g, 16.8 mmol), p-toluene sulfonic acid (0.427 g, 1.7 mmol) and 3,4-dihydro-2-H-pyran (0.985 ml, 16.8 mmol) in CH2Cl2 (30 mL) was stirred at 23° C. for 18 hours. After the addition of NaOH, the organic phase was separated, dried over MgSO4, filtered and the filtrate was concentrated in vacuo to afford the title compound as a yellow oil, (4.91 g, 95%) 1H NMR (CDCl3) δ7.6-7.5 (m, 2H), 7.35-7.2 (m, 1H), 5.37 (t, J=4.5 Hz, SCHO, 1H), 4.25-4.1 (m, CH2O, 1H), 3.7-3.55 (m, CH2O, 1H), 2.2-2.05 (m, 1H), 2.0-1.8 (m, 2H), 1.8-1.6 (m, 3H): IR 1566, 1542, 1450, 1367, 1257, 1188, 1101, 1037, 1024, 1008, 867, 809, 783 cm−1; Anal. Calcd. for C11H12BrClOS: C, 42.95; H, 3.93. Found: C,43.15; H, 3.91. the organic phase was separated dried over MgSO4 filtered the filtrate was concentrated in vacuo

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-bromo-4-chlorobenzene disulfide (3.8 g, 8.5 mmol) in THF (30 mL) was treated with NaBH4 (0.83 g, 22.0 mmol). The mixture was refluxed for a while and treated with MeOH (2 mL); heating was resumed for 0.5 hours. Mixture was cooled to 23° C., acidified with HCl (3N) and extracted with Et2O. The Et2O extracts were dried over MgSO4, filtered, and the filtrate was concentrated in vacuo to afford the title compound which was used without further purification. The mixture was refluxed for a while heating extracted with Et2O The Et2O extracts were dried over MgSO4 filtered the filtrate was concentrated in vacuo

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Potassium carbonate (0.926 g, 9.34 mmol) then bromoacetaldehyde dimethyl acetal (1.35 g, 6.85 mmol) were added to a solution of 2-bromo-4-chlorobenzenethiol (1.397 g, 6.23 mmol) in anhydrous DMF (11 mL). The mixture was heated at 70° C. for 3 hours. After being allowed to cool to room temperature, the mixture was diluted with ethyl acetate and water. The resulting layers were separated and the aqueous phase was extracted with ethyl acetate. The combined organics were washed with water then saturated NaCl (aq), dried over Na2SO4, filtered, then concentrated. The resulting light yellow oil was used directly for the following step. 1H NMR (500 MHz, CDCl3) δ 7.57 (d, J=2.0 Hz, 1H); 7.33 (d, J=8.5 Hz, 1H); 7.26 (dd, J=8.5, 2.0 Hz, 1H); 4.70 (t, J=5.5 Hz, 1H); 3.75-3.68 (m, 2H); 3.61-3.55 (m, 2H); 3.15 (d, J=5.5 Hz, 2H); 1.23 (t, 7.0 Hz, 6H). to cool to room temperature The resulting layers were separated the aqueous phase was extracted with ethyl acetate The combined organics were washed with water saturated NaCl (aq), dried over Na2SO4 filtered concentrated

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-bromo-4-chlorothiophenol (3.74 g, 16.8 mmol), p-toluene sulfonic acid (0.427 g, 1.7 mmol) and 3,4-dihydro-2-H-pyran (0.985 ml, 16.8 mmol) in CH2Cl2 (30 mL) was stirred at 23° C. for 18 hours. After the addition of NaOH, the organic phase was separated, dried over MgSO4, filtered and the filtrate was concentrated in vacuo to afford the title compound as a yellow oil, (4.91 g, 95%) 1H NMR (CDCl3) δ7.6-7.5 (m, 2H), 7.35-7.2 (m, 1H), 5.37 (t, J=4.5 Hz, SCHO, 1H), 4.25-4.1 (m, CH2O, 1H), 3.7-3.55 (m, CH2O, 1H), 2.2-2.05 (m, 1H), 2.0-1.8 (m, 2H), 1.8-1.6 (m, 3H): IR 1566, 1542, 1450, 1367, 1257, 1188, 1101, 1037, 1024, 1008, 867, 809, 783 cm−1; Anal. Calcd. for C11H12BrClOS: C, 42.95; H, 3.93. Found: C,43.15; H, 3.91. the organic phase was separated dried over MgSO4 filtered the filtrate was concentrated in vacuo

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-bromo-4-chlorobenzene disulfide (3.8 g, 8.5 mmol) in THF (30 mL) was treated with NaBH4 (0.83 g, 22.0 mmol). The mixture was refluxed for a while and treated with MeOH (2 mL); heating was resumed for 0.5 hours. Mixture was cooled to 23° C., acidified with HCl (3N) and extracted with Et2O. The Et2O extracts were dried over MgSO4, filtered, and the filtrate was concentrated in vacuo to afford the title compound which was used without further purification. The mixture was refluxed for a while heating extracted with Et2O The Et2O extracts were dried over MgSO4 filtered the filtrate was concentrated in vacuo