1-bromo-4-(2,2-dimethoxyethylsulfanyl)benzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of polyphosphoric acid (10 g) in chlorobenzene (260 mL) was heated to reflux and added, under nitrogen, dropwise in one hour 1-bromo-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12; 9.71 g, 35 mmol). The reaction mixture was then heated for 4 h until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride. Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 3.8 g of 5-bromo-benzo[b]thiophene (white solid) (Yield=51%). was heated to reflux The reaction mixture was then heated for 4 h until reaction cooled quenched with water (150 mL) extracted into methylene chloride Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of polyphosphoric acid (10 g) in chlorobenzene (260 mL) was heated to reflux and added, under nitrogen, dropwise in one hour 1-bromo-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12; 9.71 g, 35 mmol). The reaction mixture was then heated for 4 h until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride. Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 3.8 g of 5-bromo-benzo[b]thiophene (white solid) (Yield=51%). was heated to reflux The reaction mixture was then heated for 4 h until reaction cooled quenched with water (150 mL) extracted into methylene chloride Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromobenzenethiol (7.56 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-bromo4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12) (9.71 g; orange oil) (Yield=87%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromobenzenethiol (7.56 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-bromo4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12) (9.71 g; orange oil) (Yield=87%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of polyphosphoric acid (10 g) in chlorobenzene (260 mL) was heated to reflux and added, under nitrogen, dropwise in one hour 1-bromo-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12; 9.71 g, 35 mmol). The reaction mixture was then heated for 4 h until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride. Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 3.8 g of 5-bromo-benzo[b]thiophene (white solid) (Yield=51%). was heated to reflux The reaction mixture was then heated for 4 h until reaction cooled quenched with water (150 mL) extracted into methylene chloride Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of polyphosphoric acid (10 g) in chlorobenzene (260 mL) was heated to reflux and added, under nitrogen, dropwise in one hour 1-bromo-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12; 9.71 g, 35 mmol). The reaction mixture was then heated for 4 h until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride. Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 3.8 g of 5-bromo-benzo[b]thiophene (white solid) (Yield=51%). was heated to reflux The reaction mixture was then heated for 4 h until reaction cooled quenched with water (150 mL) extracted into methylene chloride Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromobenzenethiol (7.56 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-bromo-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12) (9.71 g; orange oil) (Yield=87%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of polyphosphoric acid (10 g) in chlorobenzene (260 mL) was heated to reflux and added, under nitrogen, dropwise in one hour 1-bromo-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12; 9.71 g, 35 mmol). The reaction mixture was then heated for 4 h until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride. Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 3.8 g of 5-bromo-benzo[b]thiophene (white solid) (Yield=51%). was heated to reflux The reaction mixture was then heated for 4 h until reaction cooled quenched with water (150 mL) extracted into methylene chloride Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromobenzenethiol (7.56 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-bromo4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE12) (9.71 g; orange oil) (Yield=87%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated